WO2022165726A1 - Coated rubber particle, preparation method therefor and use thereof - Google Patents

Coated rubber particle, preparation method therefor and use thereof Download PDF

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Publication number
WO2022165726A1
WO2022165726A1 PCT/CN2021/075349 CN2021075349W WO2022165726A1 WO 2022165726 A1 WO2022165726 A1 WO 2022165726A1 CN 2021075349 W CN2021075349 W CN 2021075349W WO 2022165726 A1 WO2022165726 A1 WO 2022165726A1
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Prior art keywords
parts
weight
ratio
rubber particles
atomic
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PCT/CN2021/075349
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French (fr)
Chinese (zh)
Inventor
李公让
李文博
孙丙向
田辉
王锡洲
李科
贾江鸿
于雷
孙杰
***
王承俊
李炳太
李海斌
刘振东
高凯
李春光
李卉
Original Assignee
中国石油化工股份有限公司
中石化石油工程技术服务有限公司
中石化胜利石油工程有限公司
中石化胜利石油工程有限公司钻井工艺研究院
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Priority claimed from CN202110140385.1A external-priority patent/CN114836179A/en
Priority claimed from CN202110140380.9A external-priority patent/CN114836181A/en
Priority claimed from CN202110145837.5A external-priority patent/CN114835922A/en
Application filed by 中国石油化工股份有限公司, 中石化石油工程技术服务有限公司, 中石化胜利石油工程有限公司, 中石化胜利石油工程有限公司钻井工艺研究院 filed Critical 中国石油化工股份有限公司
Priority to US17/997,074 priority Critical patent/US20230242804A1/en
Publication of WO2022165726A1 publication Critical patent/WO2022165726A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls

Definitions

  • the present invention relates to the technical field of drilling. Specifically, the present invention relates to a coated rubber particle, its manufacturing method and its application as a plugging material in drilling fluid.
  • the commonly used plugging materials mainly include bridging plugging materials, high water loss plugging materials, temporary plugging materials to protect production layers, chemical leakage plugging materials, inorganic cementing leakage plugging materials and soft (hard) leakage plugging materials according to different mechanisms and functions. ) plug-type plugging materials and other categories.
  • the application of these lost circulation materials greatly reduces the loss caused by lost circulation to a certain extent.
  • oil-based drilling fluids are usually used in the current shale oil and gas development process. Due to the special geological structure and lithological development characteristics of shale formations, lost circulation often occurs. There is a lack of special oil-based drilling fluid plugging materials, and conventional water-based drilling fluid plugging materials are still used. However, some elastic plugging materials for water-based drilling fluids are oil-soluble and will dissolve in oil-based drilling fluids, and do not have the ability to support The performance of pressure plugging is not suitable for oil-based drilling fluid plugging.
  • the inventors of the present invention also found that most of the water-based drilling fluid plugging materials are hydrophilic materials, which have poor compatibility with oil-based drilling fluids, and are easily affected by drilling fluid contamination, which affects the plugging effect or reversely affects the performance of the drilling fluid, resulting in Complicated underground accident.
  • the inventor of the present invention further found that the elastoplasticity plugging particles are usually oil-soluble, and even if oil-resistant rubber is immersed in oil-based drilling fluid for a long time, partial dissolution will occur, resulting in the decline of rubber strength, elasticity and other properties, thereby causing Failure to form effective plugging or re-leakage during drilling. It can be seen that the prior art lacks leakage plugging products with high strength, oil resistance and elastic-plastic properties. The present invention has been completed based on these findings.
  • the present invention relates to the following aspects.
  • the ratio of the high-valent metal content (atomic %) of the coating layer to the high-valent metal content (atomic %) of the inner core is 1-10 ( Preferably 1.2-3), and/or, the high-valent metal is selected from at least one of aluminum, calcium, titanium, magnesium, barium and silicon (preferably selected from at least one of calcium and silicon, especially calcium), And/or, the high-valent metal content (atomic %) of the cladding layer is 0.15-0.50% (preferably 0.20-0.30%), and/or the high-valent metal content (atomic %) of the inner core is 0.05-0.2% (preferably 0.10-0.15%), and/or, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.003-0.01 (preferably 0.004-0.008), and/or, the metal-carbon ratio B ( atomic ratio) is 0.0008-0.003 (preferably 0.001-0.002), and/or, the ratio of the metal-carbon ratio A to the metal-carbon ratio
  • the coating layer comprises inorganic particles (preferably inorganic nanoparticles, especially at least one selected from the group consisting of calcium carbonate nanoparticles, silica nanoparticles, alumina nanoparticles and silica alumina nanoparticles), and/or, the coating layer comprises a fluoropolymer (preferably fluoropolyolefins, especially selected from the group consisting of tetrafluoroethylene homopolymers, tetrafluoroethylene copolymers, vinylidene fluoride homopolymers, vinylidene fluoride copolymers, hexafluoropropylene homopolymers and hexafluoropropylene copolymers at least one of them).
  • inorganic particles preferably inorganic nanoparticles, especially at least one selected from the group consisting of calcium carbonate nanoparticles, silica nanoparticles, alumina nanoparticles and silica alumina nanoparticles
  • the coating layer comprises
  • the weight ratio of the inorganic particles to the inner core is 0.01-0.12 (preferably 0.02-0.05), and/or, the fluoropolymer
  • the weight ratio to the inner core is 0.015-0.06 (preferably 0.025-0.04), and/or the average particle size of the coated rubber particles is 0.5-20 mm (preferably 1-5 mm), and/or the inorganic particles
  • the average particle size is 10-500nm (preferably 50-300nm or 50-200nm), and/or the thickness of the coating layer is such that the coating rubber particles have a 24h oil absorption rate is reduced by more than 20% (preferably by more than 30%, more preferably by 35-60%), preferably the thickness of the coating layer is 0.05-500 microns (preferably 1-300 microns or 20-200 microns), and /or, compared with the case without the coating layer, the 24-hour oil absorption of the coated rubber particles is reduced by more than 20% (preferably by more than 30%, more preferably by 35
  • a manufacturing method of coated rubber particles comprising the following steps:
  • step (2) comprises:
  • the coating (preferably spraying or showering) is performed with the fluoropolymer, and then dried or not (preferably not dried).
  • the fluoropolymer is a fluoropolyolefin, in particular selected from the group consisting of tetrafluoroethylene homopolymer, tetrafluoroethylene copolymer, vinylidene fluoride homopolymer At least one of compounds, vinylidene fluoride copolymers, hexafluoropropylene homopolymers and hexafluoropropylene copolymers, and/or, the inorganic particles are inorganic nanoparticles, especially selected from calcium carbonate nanoparticles, carbon dioxide At least one of silicon nanoparticles, aluminum oxide nanoparticles and silicon aluminum nanoparticles, and/or, the rubber is selected from at least one of natural rubber, synthetic rubber and composite materials thereof, and/or, the rubber The particles have an average particle size of 0.5-20 mm (preferably 1-5 mm), and/or the inorganic particles have an average particle size of 10-500 nm
  • the inorganic coating composition comprises the inorganic particles, a binder (preferably a polymer emulsion, especially a polyacrylate emulsion, polyacetic acid) At least one of vinyl ester emulsion, ethyl ⁇ -cyanoacrylate emulsion, epoxy resin emulsion, polyurethane emulsion and rosin emulsion, more particularly polyvinyl acetate emulsion), optional coupling agent (preferably silane Coupling agent, more preferably at least one selected from vinyl tri-C1-6 alkoxy (preferably tri-C1-4 alkoxy) silane, especially selected from vinyl triethoxy silane, vinyl trimethoxy silane at least one of vinyl tris(beta-methoxyethoxy)silane), optional wetting agent (preferably selected from polyethylene glycols, alkyl sulfates, organic sulfonates, and polyoxyethylene glycols) At least one of
  • the inorganic coating composition comprises 10-50 parts by weight (preferably 15-25 parts by weight) of the inorganic particles, the adhesive 10-30 parts by weight (preferably 20-30 parts by weight) of a binding agent, 0-10 parts by weight (preferably 2-5 parts by weight) of the optional coupling agent, 0-10 parts by weight of the optional wetting agent parts (preferably 2-5 parts by weight), 0-10 parts by weight (preferably 2-5 parts by weight) of the optional dispersant, and 0-10 parts by weight (preferably 2-5 parts by weight) of the optional medium ), and/or, in parts by weight, the fluorine-containing coating composition comprises 3-15 parts by weight (preferably 5-10 parts by weight) of the fluoropolymer, 1-8 parts by weight of the dispersant ( Preferably 1-3 parts by weight) and 20-50 parts by weight (preferably 25-40 parts by weight) of the medium.
  • a wetting step is also included: using a wetting agent (preferably selected from carboxylic acids and alcohols) At least one in, more preferably selected from at least one in water-soluble carboxylic acid and water-soluble alcohol, especially selected from at least one in C1-6 monobasic or polyvalent carboxylic acid and C1-6 monobasic or polyhydric alcohol.
  • a wetting agent preferably selected from carboxylic acids and alcohols
  • the rubber particles are treated (preferably by spraying or spraying), more particularly at least one selected from the group consisting of acetic acid and glycerol) and then dried or not (preferably not dried).
  • wetting agent composition a composition containing the wetting agent
  • the composition includes the humectant and water.
  • the wetting agent composition comprises 2-15 parts by weight (preferably 3-10 parts by weight) of the wetting agent and water 98 -85 parts by weight (preferably 90-97 parts by weight), and/or, the weight ratio of the wetting agent to the rubber particles is 0.01-0.05 (preferably 0.02-0.035).
  • the operating conditions of the step (2-1) include: spraying or spraying method, using an ultrasonic vibrating screen, and the operating temperature is 40-85° C. (preferably 45° C.). -70°C or 55-60°C), the ultrasonic frequency is 5-100KHZ (preferably 10-50KHZ or 20-30KHZ), the vibration frequency is 10-100HZ (preferably 25-75HZ or 45-55HZ), and the air pressure of the spray gun is 0.1- 0.5MPaG (preferably 0.2-0.3MPaG), the diameter of the nozzle is 2-20mm (preferably 5-10mm), and/or, the operating conditions of the step (2-2) include: spraying or spraying method, using a vibrating screen, The operating temperature is 20-45°C (preferably 30-35°C), the vibration frequency is 10-100HZ (preferably 25-75HZ or 45-55HZ), the air pressure of the spray gun is controlled at 0.1-0.5MPaG (preferably 0.2-0.3MP
  • a drilling fluid composition (preferably an oil-based drilling fluid composition) comprising a lost circulation material and a base slurry (such as selected from the group consisting of white oil-based drilling fluid base slurry, diesel-based drilling fluid base slurry, and synthetic-based drilling fluid base slurry At least one of the above-mentioned or later), wherein the loss-stopping material comprises or is the coated rubber particles described in any one of the foregoing or later described or the coated rubber particles manufactured according to any one of the foregoing or later described manufacturing methods.
  • a base slurry such as selected from the group consisting of white oil-based drilling fluid base slurry, diesel-based drilling fluid base slurry, and synthetic-based drilling fluid base slurry At least one of the above-mentioned or later
  • the loss-stopping material comprises or is the coated rubber particles described in any one of the foregoing or later described or the coated rubber particles manufactured according to any one of the foregoing or later described manufacturing methods.
  • the mass percentage of the coated rubber particles is 2-12 wt % ( preferably 3-8 wt%).
  • FIG. 1 is an SEM photograph of the coated rubber particles produced in Example 5.
  • FIG. 1 is an SEM photograph of the coated rubber particles produced in Example 5.
  • FIG. 2 is an EDS spectrum of the coated rubber particles produced in Example 5.
  • the coated rubber particles of the present invention compared with the leakage plugging materials in the prior art, the oil resistance performance is better, the strength is higher, and the elastic deformation ability and the plugging performance. Therefore, by using its pressure and temperature deformation properties, it is possible to effectively form accumulation plugging layers in formation fractures and pore throats, so as to achieve effective plugging of fractures and leakage layers.
  • the rubber core will be deformed under the condition of the bottom hole, and the coating layer (especially the inert particles) coated on the surface of the core will not fall off, and will stick closely to the surface of the rubber core. , thereby preventing the rubber particle core from dissolving in the oil phase.
  • coated rubber particles according to the present invention have a coating layer, especially when the coating layer contains inorganic particles, the strength of the rubber core can be greatly enhanced, and the pressure bearing capacity is higher.
  • coated rubber particles according to the present invention can elastically deform under temperature or pressure conditions, squeeze into the pores and seams for pressure-bearing sealing, and the coating layer can be adsorbed and cemented with the formation to improve the retention capacity, and the sealing effect of pores and seams is good.
  • substantially means to allow for deviations that are acceptable or reasonable to those skilled in the art, such as deviations within ⁇ 10%, ⁇ 5%, or ⁇ 2%.
  • the measurement conditions for SEM photos and EDS spectra include: Field Emission Scanning Electron Microscope (JEOL, Japan, model JSM-7200F), 10.0KV, magnification of 5000 times, using the electron microscope with its own energy spectrum scanner Test the surface of the sample, automatically calculate and output the mass percentage measurement results. Samples were thoroughly dried prior to measurement. Before measurement, the sample was cut, and a conductive layer was sprayed on the cut section in a vacuum coater, and then the sample was adhered to the sample table with conductive double-sided tape, and then sent to the electron microscope for measurement.
  • Field Emission Scanning Electron Microscope JEOL, Japan, model JSM-7200F
  • magnification of 5000 times using the electron microscope with its own energy spectrum scanner Test the surface of the sample, automatically calculate and output the mass percentage measurement results. Samples were thoroughly dried prior to measurement. Before measurement, the sample was cut, and a conductive layer was sprayed on the cut section in a vacuum coater, and then the sample was adhered to the sample table
  • any two or more embodiments of the present invention can be combined arbitrarily, and the technical solutions formed thereby belong to a part of the original disclosure content of this specification, and also fall within the protection scope of the present invention.
  • the present invention relates to a coated rubber particle having a rubber core and a coating layer.
  • the coated rubber particles have good oil resistance, and are particularly suitable for use in drilling fluids, especially oil-based drilling fluids, as a plugging material.
  • the fluorine element content (at %) of the inner core is generally 0-15%, preferably 0-8%.
  • the fluorine element content of the inner core was measured by SEM and EDS spectroscopy.
  • the fluorine element content (atomic %) of the coating layer is generally 30-80%, preferably 40-65%.
  • the fluorine element content of the coating layer was measured by SEM and EDS spectroscopy.
  • the 24-hour oil absorption of the coated rubber particles is generally below 4%, preferably below 3%, more preferably 1.5-2.5%.
  • the inventors of the present invention believe that such a low 24h oil absorption rate cannot be achieved by the plugging materials in the prior art.
  • the high-valent metal content (atomic %) of the coating layer is 0.15-0.50%, preferably 0.20-0.30%.
  • the high-valent metal content of the coating layer was measured by SEM and EDS spectroscopy.
  • the high-valent metal content (at %) of the inner core is 0.05-0.2%, preferably 0.10-0.15%.
  • the high-valent metal content of the inner core was measured by SEM and EDS spectroscopy.
  • the high-valent metal is selected from at least one of aluminum, calcium, titanium, magnesium, barium and silicon, preferably selected from at least one of calcium and silicon, especially calcium.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is generally 1-10, preferably 1.2-3.
  • the metal-to-carbon ratio (atomic ratio, referred to as metal-to-carbon ratio A) of the coating layer is 0.003-0.01, preferably 0.004-0.008.
  • the metal-to-carbon ratio of the cladding layer was measured by SEM and EDS spectroscopy.
  • the metal-to-carbon ratio (atomic ratio, referred to as metal-to-carbon ratio B) of the inner core is 0.0008-0.003, preferably 0.001-0.002.
  • the metal-to-carbon ratio of the inner core was measured by SEM and EDS spectroscopy.
  • the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 2-13, preferably 3-6.
  • the fluorocarbon ratio (atomic ratio) of the coating layer is 1-3, preferably 1.2-1.8.
  • the fluorocarbon ratio of the coating layer was measured by SEM and EDS spectroscopy.
  • the fluorocarbon ratio (atomic ratio) of the inner core is 0-0.25, preferably 0-0.12.
  • the fluorocarbon ratio of the inner core was measured by SEM and EDS spectroscopy.
  • the rubber is selected from at least one of natural rubber, synthetic rubber and composite materials thereof.
  • the rubber may be virgin rubber or waste rubber, and the latter is preferred from the viewpoint of cost.
  • the coating layer comprises inorganic particles.
  • inorganic nanoparticles are preferred, especially at least one selected from the group consisting of calcium carbonate nanoparticles, silica nanoparticles, alumina nanoparticles, and silicon-alumina nanoparticles.
  • the cladding layer comprises a fluoropolymer.
  • a fluorinated polyolefin is preferable, and is especially selected from the group consisting of tetrafluoroethylene homopolymer, tetrafluoroethylene copolymer, vinylidene fluoride homopolymer, vinylidene fluoride copolymer, hexafluoropropylene At least one of a homopolymer and a hexafluoropropylene copolymer.
  • the weight ratio of the inorganic particles to the inner core is 0.01-0.12, preferably 0.02-0.05.
  • the weight ratio of the fluoropolymer to the inner core is 0.015-0.06, preferably 0.025-0.04.
  • the average particle size of the coated rubber particles is generally 0.5-20 mm, preferably 1-5 mm.
  • the coated rubber particles of the present invention may be in any shape such as spherical, flake, and square, or may be in any irregular shape, and are not particularly limited.
  • the average particle size of the coated rubber particles generally refers to the average value of the sum of the length, width and height, or the average value of the largest size and the smallest size, or the equivalent diameter of the particles.
  • the average particle size of the inorganic particles is 10-500 nm, preferably 50-300 nm or 50-200 nm.
  • the average particle size of the inorganic particles is measured by dynamic light scattering nanoparticle size distribution measurement.
  • the coating layer in the coated rubber particles, may be continuous, that is, cover the entire surface of the inner core, or discontinuous, that is, only cover the inner core. Some of them are not particularly limited. However, from the viewpoint that the technical effect of the present invention is more excellent, it is preferably continuous or substantially continuous.
  • the thickness of the coating layer is not particularly limited, as long as a substance layer is formed within a range commonly understood by those skilled in the art. From the viewpoint of achieving more excellent technical effects of the present invention, the thickness of the coating layer reduces the 24-hour oil absorption rate of the coated rubber particles by more than 20% compared with the case without the coating layer, A reduction of more than 30% is preferred, and a reduction of 35-60% is more preferred.
  • the thickness of the coating layer is generally 0.05-500 microns, preferably 1-300 microns or 20-200 microns.
  • the thickness refers to the average thickness of the cladding layer, and the measurement method includes: selecting any 20 points on the SEM photo, and taking the average value is the average thickness of the cladding layer.
  • the 24-hour oil absorption rate of the coated rubber particles is reduced by more than 20%, preferably by more than 30%, and more preferably by 35-60%.
  • the present invention also relates to a method for manufacturing coated rubber particles.
  • the manufacturing method can be used to manufacture the coated rubber particles of the present invention.
  • the manufacturing method of the coated rubber particles comprises the following steps:
  • the weight ratio of the inorganic particles to the rubber particles is generally 0.01-0.12, preferably 0.02-0.05.
  • the weight ratio of the fluoropolymer to the rubber particles is generally 0.015-0.06, preferably 0.025-0.04.
  • one of inorganic particles and fluoropolymer may be used, or both materials may be used, preferably both materials are used. use.
  • the coating in the step (2), can be performed in any manner and method conventionally known in the art, as long as the coating (preferably uniform coating) on the surface of the rubber particles can be achieved coating), but from the viewpoint of coating uniformity, spraying or spraying is preferred.
  • the rubber particles are selected from at least one of natural rubber particles, synthetic rubber particles and composite material particles thereof.
  • the rubber particles include waste rubber particles, ie particles made from waste rubber.
  • the oil absorption rate of the rubber particles in 24 hours before coating is generally 4-6%, and the oil absorption rate in 24 hours after coating can generally be reduced to below 4%, preferably below 3%, more It is preferably reduced to 1.5-2.5%.
  • the step (2) includes a step (2-1): coating with the inorganic particles, and then drying or not drying, preferably not drying.
  • the coating in the step (2-1), can be performed in any manner and method conventionally known in the art, as long as the coating on the surface of the rubber particles can be achieved (preferably Uniform coating) is sufficient, but from the viewpoint of coating uniformity, spraying or spraying is preferred.
  • the ultrasonic frequency is 5-100KHZ, preferably 10-50KHZ or 20-30KHZ, and the vibration frequency is 10-100HZ, preferably 25-75HZ or 45-55HZ.
  • the operating temperature is 40-85°C, preferably 45-70°C or 55-60°C.
  • the air pressure of the spray gun is controlled to be 0.1-0.5 MPaG, preferably 0.2-0.3 MPaG, and the diameter of the nozzle is 2-20 mm, preferably 5-10 mm.
  • the step (2) includes a step (2-2): coating with the fluoropolymer, and then drying or not drying, preferably not drying.
  • the coating in the step (2-2), can be performed in any manner and method conventionally known in the art, as long as the coating on the surface of the rubber particles can be achieved (preferably Uniform coating) is sufficient, but from the viewpoint of coating uniformity, spraying or spraying is preferred.
  • the vibration frequency is generally 10-100HZ, preferably 25-75HZ or 45-55HZ, without ultrasound or using ultrasound, the ultrasound frequency at this time is generally 5-100KHZ, preferably 10-50KHZ or 20-30KHZ.
  • the operating temperature is 20-45°C, preferably 30-35°C.
  • the air pressure of the spray gun is controlled to be 0.1-0.5 MPaG, preferably 0.2-0.3 MPaG, and the nozzle diameter is 2 -20mm, preferably 5-10mm.
  • the step (2-2) may be performed before the step (2-1), may be performed simultaneously with the step (2-1), or may be performed after the step (2-1). -1), preferably after the step (2-1).
  • the fluoropolymer is a fluoropolyolefin, in particular selected from the group consisting of tetrafluoroethylene homopolymer, tetrafluoroethylene copolymer, vinylidene fluoride homopolymer , at least one of vinylidene fluoride copolymer, hexafluoropropylene homopolymer and hexafluoropropylene copolymer.
  • the inorganic particles are inorganic nanoparticles, in particular selected from calcium carbonate nanoparticles, silica nanoparticles, alumina nanoparticles and silicon aluminum nanoparticles at least one.
  • the average particle size of the rubber particles is generally 0.5-20 mm, preferably 1-5 mm.
  • the rubber particles may be in any shape such as spherical, flake, and square, or may be in any irregular shape, and are not particularly limited.
  • the average particle size of the rubber particles generally refers to the average value of the sum of their length, width and height, or the average value of their largest and smallest dimensions, or the equivalent diameter of the particles.
  • the average particle size of the inorganic particles is 10-500 nm, preferably 50-300 nm or 50-200 nm.
  • the average particle size of the inorganic particles is measured by dynamic light scattering nanoparticle size distribution measurement.
  • the inorganic particles are used in the form of a coating composition (referred to as an inorganic coating composition) containing the inorganic particles.
  • the inorganic coating composition generally comprises the inorganic particles, a binder, an optional coupling agent, an optional wetting agent, an optional dispersing agent, and an optional vehicle.
  • the binder is not particularly limited, and those conventionally known in the art may be used.
  • Specific examples of the binder include polymer emulsions, especially selected from polyacrylate emulsions, polyvinyl acetate emulsions, ⁇ -cyanoacrylate ethyl ester emulsions, epoxy resin emulsions, polyurethane emulsions and At least one of rosin latex, more particularly polyvinyl acetate based latex.
  • the coupling agent is not particularly limited, and those conventionally known in the art can be used.
  • Specific examples of the coupling agent include silane coupling agents, preferably at least one selected from vinyltri-C1-6 alkoxy (preferably tri-C1-4 alkoxy) silanes, especially selected from At least one of vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris(beta-methoxyethoxy)silane.
  • the wetting agent is not particularly limited, and those conventionally known in the art can be used.
  • Specific examples of the wetting agent include at least one selected from polyethylene glycols, alkyl sulfates, organic sulfonates and polyoxyethylene ethers, more preferably polyethylene glycols and alkyl sulfates at least one of the salts.
  • the dispersing agent is not particularly limited, and those conventionally known in the art may be used.
  • Specific examples of the dispersing agent include at least one selected from the group consisting of polyacrylates, cellulose derivatives, polyacrylamides, and polyoxyethylene ether phosphates, and more preferably, sodium cellulose sulfate.
  • the medium is not particularly limited, and those conventionally known in the art can be used.
  • Specific examples of the medium include water.
  • the inorganic coating composition comprises 10-50 parts by weight (preferably 15-25 parts by weight) of the inorganic particles, the adhesive 10-30 parts by weight (preferably 20-30 parts by weight) of the optional coupling agent, 0-10 parts by weight (preferably 2-5 parts by weight) of the optional coupling agent, 0-10 parts by weight of the optional wetting agent (preferably 2-5 parts by weight), 0-10 parts by weight (preferably 2-5 parts by weight) of the optional dispersant, and 0-10 parts by weight (preferably 2-5 parts by weight) of the optional medium .
  • the fluoropolymer in the manufacturing method, is used in the form of a coating composition containing the fluoropolymer (referred to as a fluorine-containing coating composition).
  • the fluorine-containing coating composition includes at least the fluorine-containing polymer, a dispersant and a vehicle.
  • specific examples of the medium include water.
  • the dispersant in the fluorine-containing coating composition, is not particularly limited, and those conventionally known in the art can be used.
  • Specific examples of the dispersing agent include surfactants, particularly at least one selected from potassium perfluorooctanesulfonate and ammonium perfluorooctanoate, and potassium perfluorooctanesulfonate is more preferred.
  • the fluorine-containing coating composition in parts by weight, comprises 3-15 parts by weight (preferably 5-10 parts by weight) of the fluoropolymer, the 1-8 parts by weight (preferably 1-3 parts by weight) of the dispersant and 20-50 parts by weight (preferably 25-40 parts by weight) of the medium.
  • a wetting step is further included between the step (1) and the step (2).
  • the rubber particles are treated with a wetting agent and then dried or not, preferably not dried.
  • the weight ratio of the wetting agent to the rubber particles is 0.01-0.05, preferably 0.02-0.035.
  • the treatment in the wetting step, may be performed in any manner and method conventionally known in the art, as long as the coating (preferably uniform coating) of the surface of the rubber particles can be achieved. Any, but from the viewpoint of coating uniformity, spraying or showering is preferable.
  • the wetting agent for example, at least one selected from carboxylic acids and alcohols can be cited, more preferably selected from water-soluble carboxylic acids and water At least one of readily soluble alcohols, in particular at least one selected from C1-6 mono- or polycarboxylic acids and C1-6 mono- or polyhydric alcohols, more particularly at least one selected from acetic acid and glycerol.
  • the wetting agent in the wetting step, is used in the form of a composition containing the wetting agent (referred to as a wetting agent composition).
  • a wetting agent composition generally comprises the humectant and water.
  • the wetting agent composition in parts by weight, comprises 2-15 parts by weight (preferably 3-10 parts by weight) of the wetting agent and 98-85 parts by weight (preferably 90-10 parts by weight) of water 97 parts by weight).
  • the manufacturing method of the coated rubber particles includes: (1) cleaning and drying the rubber particles; (2) successively using an acetic acid solution with a mass fraction of 8% and a acrylic acid solution with a mass fraction of 5%
  • the triol solution sprays the rubber particles, and the rubber particles are constantly turned during the spraying process to ensure that the surface of all the rubber particles is fully wetted; (3)
  • the wetted rubber particles are placed on a temperature-controlled ultrasonic vibrating screen, and the screen mesh is smaller than (4)
  • the present invention also relates to a drilling fluid composition, which comprises a lost circulation material and a base slurry.
  • the loss-stopping material includes or is the coated rubber particles described in any of the previous or later embodiments of this specification, or, the leakage-stopping material includes or is any of the foregoing or later embodiments of this specification.
  • the coated rubber particles manufactured by the manufacturing method.
  • an oil-based drilling fluid composition is preferable.
  • any base slurry conventionally used in drilling fluid compositions in the art can be used, and there is no particular limitation, but oil-based drilling fluid base slurry is preferred, and more specifically For example, at least one selected from the group consisting of white oil-based drilling fluid-based slurry, diesel-based drilling-fluid-based slurry, and synthetic-based drilling fluid-based slurry.
  • the mass percentage of the coated rubber particles is 2-12 wt %, preferably 3-8 wt %.
  • the drilling fluid composition may further include other components conventionally added in the drilling fluid composition in the art, and is not particularly limited.
  • the fibrous material is bamboo fiber (0.1-0.2 mm in diameter, 3-10 mm in length), the rubber particles A are natural rubber particles (average particle size is 1-3 mm), and the rubber particles B are It is styrene-butadiene rubber particles (average particle size is 3-5mm).
  • the composition of oil-based drilling fluid is diesel oil + 25% brine + 3% emulsifier + 2% wetting agent + 1% calcium oxide + 2% oxidized asphalt.
  • the inorganic coating composition comprises calcium carbonate nanoparticles with D90 of 75nm 15 parts, 20 parts of polyacrylate emulsion, 2 parts of vinyltriethoxysilane, 2 parts of polyethylene glycol, 2 parts of polyacrylate, and 2 parts of water, the coating operating conditions are the use of ultrasonic vibrating screen, the operating temperature is 40°C, the ultrasonic frequency is 10KHZ, the vibration frequency is 20HZ, the air pressure of the spray gun is controlled at 0.1MPaG, and the diameter of the nozzle is 20mm; the fluorine-containing coating composition, in parts by weight, comprises 3 parts of tetrafluoroethylene homopolymer, 3 parts of perfluorooctane 1 part of potassium sulfonate and 20 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 30°C, the vibration frequency
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 2.33 mm, the thickness of the coating layer was 236.3 microns, the fluorine element content (atomic %) of the inner core was 0%, and the fluorine element content (atomic %) of the coating layer was 0%. %) was 53.5%, and the 24h oil absorption rate of the coated rubber particles was 3.2%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 3.6, the high-valent metal content (atomic %) of the cladding layer is 0.18%, and the high-valent metal content (atomic %) of the inner core is 0.05%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.004, the metal-carbon ratio B (atomic ratio) of the inner core is 0.001, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 4, the cladding
  • the fluorocarbon ratio (atomic ratio) of the layer was 1.20, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.
  • the inorganic coating composition in parts by weight, comprises calcium carbonate nanoparticles with a D90 of 75nm 18 parts of particles, 25 parts of polyvinyl acetate emulsion, 4 parts of vinyltrimethoxysilane, 3 parts of alkyl sulfate, 4 parts of cellulose derivatives, and 5 parts of water, and the coating operation condition is to use an ultrasonic vibrating screen , the operating temperature is 50°C, the ultrasonic frequency is 30KHZ, the vibration frequency is 30HZ, the air pressure of the spray gun is 0.5MPaG, and the diameter of the nozzle is 5mm; 2 parts of potassium fluorooctane sulfonate and 30 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 40 ° C, the vibration frequency is 50 Hz, the air pressure of the spray gun is controlled to 0.5 MPaG,
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 2.56 mm, the thickness of the coating layer was 349.7 microns, the fluorine element content (atomic %) of the inner core was 1.5%, and the fluorine element content (atomic %) of the coating layer was 1.5%. %) was 60.7%, and the 24h oil absorption rate of the coated rubber particles was 2.8%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 3, the high-valent metal content (atomic %) of the cladding layer is 0.24%, and the high-valent metal content (atomic %) of the inner core is 0.24% is 0.08%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0063, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0016, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.94.
  • the fluorocarbon ratio (atomic ratio) of the layer was 1.60, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.03.
  • the inorganic coating composition in parts by weight, contains silica nanoparticles with D90 of 136nm 15 parts, 20 parts of polyacrylate emulsion, 2 parts of vinyltrimethoxysilane, 3 parts of polyoxyethylene ether, 1 part of polyacrylamide, and 4 parts of water, the coating operating conditions are the use of ultrasonic vibrating screen, the operating temperature is 60°C, the ultrasonic frequency is 50KHZ, the vibration frequency is 75HZ, the air pressure of the spray gun is controlled at 0.2MPaG, and the diameter of the nozzle is 10mm; the fluorine-containing coating composition, by weight, comprises 12 parts of tetrafluoroethylene copolymer and 2 parts of ammonium perfluorooctanoate And 30 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 40°C, the vibration frequency is 50HZ, the air pressure control of the
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 2.38 mm, the thickness of the coating layer was 193.7 microns, the fluorine element content (atomic %) of the inner core was 4.2%, and the fluorine element content (atomic %) of the coating layer was 4.2%. %) was 68.1%, and the 24h oil absorption rate of the coated rubber particles was 1.8%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 3.6, the high-valent metal content (atomic %) of the cladding layer is 0.26%, and the high-valent metal content (atomic %) of the inner core is 0.26% is 0.08%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0092, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0029, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.17, the cladding
  • the fluorocarbon ratio (atomic ratio) of the layer was 2.4, and the fluorocarbon ratio (atomic ratio) of the core was 0.15.
  • the inorganic coating composition in parts by weight, contains D90 of 136nm silicon dioxide nanometers 25 parts of particles, 25 parts of epoxy resin emulsion, 10 parts of vinyl tris( ⁇ -methylethoxy) silane, 2 parts of organic sulfonate, 2 parts of polyoxyethylene ether phosphate, and 5 parts of water, coated with
  • the coating operating conditions are to use an ultrasonic vibrating screen, the operating temperature is 60 °C, the ultrasonic frequency is 50KHZ, the vibration frequency is 60HZ, the air pressure of the spray gun is controlled to be 0.3MPaG, and the diameter of the nozzle is 8mm; 10 parts of fluoropropylene homopolymer, 5 parts of ammonium perfluorooctanoate and 30 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 35°C, the vibration frequency is 55H
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 4.67 mm, the thickness of the coating layer was 138.3 microns, the fluorine element content (atomic %) of the inner core was 11.5%, and the fluorine element content (atomic %) of the coating layer was 11.5%. %) was 67.5%, and the 24h oil absorption rate of the coated rubber particles was 2.3%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2.31, the high-valent metal content (atomic %) of the cladding layer is 0.30%, and the high-valent metal content (atomic %) of the inner core is 0.12%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0098, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0025, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.92.
  • the fluorocarbon ratio (atomic ratio) of the layer was 2.2, and the fluorocarbon ratio (atomic ratio) of the core was 0.24.
  • the inorganic coating composition in parts by weight, contains aluminum oxide nanoparticles with a D90 of 185nm.
  • the coating operating conditions are the use of ultrasonic vibrating screen, and the operating temperature is 85°C, the ultrasonic frequency is 100KHZ, the vibration frequency is 80HZ, the air pressure of the spray gun is controlled at 0.4MPaG, and the diameter of the nozzle is 4mm;
  • the fluorine-containing coating composition in parts by weight, comprises 10 parts of vinylidene fluoride homopolymer, perfluorooctyl 4 parts of potassium sulfonate and 40 parts of water, the coating operating conditions are vibrating screen, operating temperature is 45°C, vibration frequency is 40HZ, air pressure control of spray gun is 0.4MPaG, nozzle diameter is 4mm, and ultrasonic frequency is 100KHZ.
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 3.96 mm, the thickness of the coating layer was 63.7 microns, the fluorine element content (atomic %) of the inner core was 5.94%, and the fluorine element content (atomic %) of the coating layer was 5.94%. %) was 60.23%, and the 24h oil absorption rate of the coated rubber particles was 2.7%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2.09, the high-valent metal content (atomic %) of the cladding layer is 0.23%, and the high-valent metal content (atomic %) of the inner core is 0.11%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0063, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0015, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 4.2, the cladding
  • the fluorocarbon ratio (atomic ratio) of the layer was 1.66, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.08.
  • Example 5 The SEM photo of the coated rubber particles produced in Example 5 is shown in Figure 1, and the coating layer and the rubber core can be clearly distinguished. Two positions 1 and 2 are selected for the cladding layer, and one position 3 is selected for the rubber core. Figure 2 shows the EDS energy spectrum data of these three positions.
  • the inorganic coating composition in parts by weight, contains D90 as 30 parts of 36nm calcium carbonate nanoparticles, 30 parts of ethyl alpha-cyanoacrylate emulsion, 8 parts of vinyltriethoxysilane, 8 parts of alkyl sulfate, 6 parts of polyacrylamide, and 10 parts of water, coated
  • the operating conditions are to use an ultrasonic vibrating screen, the operating temperature is 60°C, the ultrasonic frequency is 50KHZ, the vibration frequency is 35HZ, the air pressure of the spray gun is 0.4MPaG, and the diameter of the nozzle is 4mm; the fluorine-containing coating composition is based on parts by weight.
  • the coating operating conditions are using a vibrating screen, the operating temperature is 35°C, the vibration frequency is 45HZ, the air pressure of the spray gun is controlled to 0.4MPaG, and the diameter of the nozzle is is 4mm, and the ultrasonic frequency is 50KHZ.
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 2.46 mm.
  • the thickness of the coating layer was 273.8 microns. ) was 63.2%, and the 24h oil absorption rate of the coated rubber particles was 2.5%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core was 3.09, the high-valent metal content (atomic %) of the cladding layer was 0.34%, and the high-valent metal content (atomic %) of the inner core was 0.34% is 0.11%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0099, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0027, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.67.
  • the fluorocarbon ratio (atomic ratio) of the layer was 1.84, and the fluorocarbon ratio (atomic ratio) of the core was 0.09.
  • the inorganic coating composition in parts by weight, contains D90 as 20 parts of calcium carbonate nanoparticles of 36 nm, 20 parts of polyvinyl acetate emulsion, 5 parts of vinyltrimethoxysilane, 5 parts of alkyl sulfate, 5 parts of polyacrylate, and 5 parts of water, and the coating operation conditions are: Using an ultrasonic vibrating screen, the operating temperature is 50°C, the ultrasonic frequency is 50KHZ, the vibration frequency is 35HZ, the air pressure of the spray gun is controlled to 0.3MPaG, and the diameter of the nozzle is 8mm; the fluorine-containing coating composition is based on parts by weight, comprising tetrafluoroethylene homopolymer 8 parts of materials, 3 parts of potassium perfluorooctane sulfonate and 30 parts of water
  • the content of fluorine element in the inner core (at %) is 3.9%
  • the content of fluorine element in the coating layer (at %) is 68.1%
  • the 24h oil absorption rate of the coated rubber particles is 1.8%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2.9, the high-valent metal content (atomic %) of the cladding layer is 0.29%, and the high-valent metal content (atomic %) of the inner core is 0.10%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0099, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0021, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 4.71, the cladding
  • the fluorocarbon ratio (atomic ratio) of the layer was 2.33, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.08.
  • the inorganic coating composition is based on parts by weight, comprising silicon-alumina nanometers with D90 of 167nm 18 parts of particles, 15 parts of polyacrylate emulsion, 4 parts of vinyl tris ( ⁇ -methoxyethoxy) silane, 4 parts of polyethylene glycol, 3 parts of polyacrylate, and 5 parts of water, coating operating conditions
  • the operating temperature is 60°C
  • the ultrasonic frequency is 20KHZ
  • the vibration frequency is 30HZ
  • the air pressure of the spray gun is controlled to be 0.2MPaG
  • the diameter of the nozzle is 10mm
  • the coating operation conditions are to use a vibrating screen, the operating temperature is 30 ° C, the vibration frequency is 30 Hz, the air pressure of the spray
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 2.17 mm, the thickness of the coating layer was 269.2 microns, the fluorine element content (atomic %) of the inner core was 5.3%, and the fluorine element content (atomic %) of the coating layer was 5.3%. %) was 54.9%, and the 24h oil absorption rate of the coated rubber particles was 2.6%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2.25, the high-valent metal content (atomic %) of the cladding layer is 0.27%, and the high-valent metal content (atomic %) of the inner core is 0.12%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0064, the metal-carbon ratio B (atomic ratio) of the inner core is 0.003, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 2.13.
  • the fluorocarbon ratio (atomic ratio) of the layer was 1.3, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.13.
  • the inorganic coating composition comprises calcium carbonate nanoparticles with a D90 of 75nm 25 parts of particles, 20 parts of polyvinyl acetate emulsion, 5 parts of rosin latex, 5 parts of vinyltriethoxysilane, 5 parts of polyethylene glycol, 3 parts of polyacrylate, and 8 parts of water, coating operation conditions
  • the operating temperature is 70°C
  • the ultrasonic frequency is 20KHZ
  • the vibration frequency is 45HZ
  • the air pressure of the spray gun is controlled to be 0.3MPaG
  • the diameter of the nozzle is 8mm
  • the coating operating conditions are using a vibrating screen
  • the operating temperature is 30 ° C
  • the vibration frequency is 45HZ
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 2.83 mm, the thickness of the coating layer was 177.6 microns, the fluorine element content (atomic %) of the inner core was 6.3%, and the fluorine element content (atomic %) of the coating layer was 6.3%. %) was 57.8%, and the 24h oil absorption rate of the coated rubber particles was 1.7%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core was 6.17, the high-valent metal content (atomic %) of the cladding layer was 0.37%, and the high-valent metal content (atomic %) of the inner core is 0.06%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0096, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0021, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 4.57, the cladding
  • the fluorocarbon ratio (atomic ratio) of the layer was 1.5, and the fluorocarbon ratio (atomic ratio) of the core was 0.22.
  • the inorganic coating composition in parts by weight, contains D90 22 parts of 136nm silica nanoparticles, 25 parts of polyacrylate emulsion, 3 parts of vinyltriethoxysilane, 3 parts of alkyl sulfate, 4 parts of sodium cellulose sulfate, and 5 parts of water, coated
  • the operating conditions are to use an ultrasonic vibrating screen, the operating temperature is 45°C, the ultrasonic frequency is 10KHZ, the vibration frequency is 20HZ, the air pressure of the spray gun is controlled at 0.2MPaG, and the diameter of the nozzle is 10mm; the fluorine-containing coating composition is based on parts by weight.
  • the coating operating conditions are using a vibrating screen, the operating temperature is 30°C, the vibration frequency is 40HZ, the air pressure control of the spray gun is 0.2MPaG, the diameter of the nozzle is 10mm, and the ultrasonic frequency is 20KHZ.
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 2.58 mm, the thickness of the coating layer was 257.4 microns, the fluorine element content (atomic %) of the inner core was 5.9%, and the fluorine element content (atomic %) of the coating layer was 5.9%. %) was 61.1%, and the 24h oil absorption rate of the coated rubber particles was 2.3%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2, the high-valent metal content (atomic %) of the cladding layer is 0.26%, the high-valent metal content of the inner core (atomic %) is 0.13%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0072, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0026, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 2.77.
  • the fluorocarbon ratio (atomic ratio) of the layer was 1.7, and the fluorocarbon ratio (atomic ratio) of the core was 0.12.
  • the inorganic coating composition comprises calcium carbonate nanoparticles with D90 of 75nm 15 parts, 20 parts of polyacrylate emulsion, 2 parts of vinyltriethoxysilane, 2 parts of polyethylene glycol, 2 parts of polyacrylate, and 2 parts of water, the coating operating conditions are the use of ultrasonic vibrating screen, the operating temperature The temperature is 40°C, the ultrasonic frequency is 10KHZ, the vibration frequency is 20HZ, the air pressure of the spray gun is controlled to 0.1MPaG, and the diameter of the nozzle is 20mm.
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 2.77 mm, the thickness of the coating layer was 74.6 microns, and the 24-hour oil absorption rate of the coated rubber particles was 5.7%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core was 3.5, the high-valent metal content (atomic %) of the cladding layer was 0.14%, and the high-valent metal content (atomic %) of the inner core was 0.14%.
  • the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0042, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0013, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.23.
  • the fluorine-containing coating composition in parts by weight, contains 3 parts of tetrafluoroethylene homopolymer , 1 part of potassium perfluorooctane sulfonate and 20 parts of water, the coating operating conditions are to use a vibrating screen, the operating temperature is 30 ° C, the vibration frequency is 40HZ, the air pressure control of the spray gun is 0.1MPaG, the diameter of the nozzle is 20mm, and the ultrasonic frequency is 20KHZ.
  • the obtained coated rubber particles were analyzed and tested, and the average particle size was 2.62 mm, the thickness of the coating layer was 217.5 microns, the fluorine element content (atomic %) of the inner core was 0%, and the fluorine element content (atomic %) of the coating layer was 0%. %) was 63.3%, and the 24h oil absorption rate of the coated rubber particles was 3.9%.
  • the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2.2, the high-valent metal content (atomic %) of the cladding layer is 0.11%, and the high-valent metal content (atomic %) of the inner core is 0.11% is 0.05%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0031, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0008, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.88, the cladding
  • the fluorocarbon ratio (atomic ratio) of the layer was 1.81, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.
  • Example 1 The coated rubber particles prepared in Example 1 with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based drilling fluid for plugging losses.
  • Example 9 The coated rubber particles prepared in Example 9 with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based drilling fluid for plugging losses.
  • Example 6 The coated rubber particles prepared in Example 6 with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based lost circulation plugging drilling fluid.
  • Example 2 The coated rubber particles prepared in Example 2 with a mass fraction of 3% and the coated rubber particles prepared in Example 3 with a mass fraction of 2% were added to the oil-based drilling fluid to obtain an oil-based plugging drilling fluid.
  • Example 3 The coated rubber particles prepared in Example 3 with a mass fraction of 3% and the coated rubber particles prepared in Example 4 with a mass fraction of 2% were added to the oil-based drilling fluid to obtain an oil-based plugging drilling fluid.
  • Example 4 The coated rubber particles prepared in Example 4 with a mass fraction of 3% and the coated rubber particles prepared in Example 5 with a mass fraction of 2% were added to the oil-based drilling fluid to obtain an oil-based plugging drilling fluid.
  • Example 5 The coated rubber particles prepared in Example 5 with a mass fraction of 3% and fibrous materials with a mass fraction of 2% were added to the oil-based drilling fluid to obtain an oil-based lost circulation plugging drilling fluid.
  • Example 6 The coated rubber particles prepared in Example 6 with a mass fraction of 3% and fibrous materials with a mass fraction of 2% were added to the oil-based drilling fluid to obtain an oil-based lost circulation plugging drilling fluid.
  • Example 7 To the oil-based drilling fluid, the coated rubber particles prepared in Example 7 with a mass fraction of 2%, the coated rubber particles prepared in Example 8 with a mass fraction of 2%, and a fibrous material with a mass fraction of 1% were added , to obtain oil-based plugging drilling fluid.
  • the coated rubber particles prepared in Example 10 with a mass fraction of 3%, the coated rubber particles prepared in Example 7 with a mass fraction of 1%, and fibrous materials with a mass fraction of 1% were added to the oil-based drilling fluid , to obtain oil-based plugging drilling fluid.
  • Example 11 The coated rubber particles prepared in Example 11 with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based lost circulation plugging drilling fluid.
  • Example 12 The coated rubber particles prepared in Example 12 with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based lost circulation plugging drilling fluid.
  • the rubber particles A with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based lost circulation plugging drilling fluid.
  • the plugging performance of the oil-based plugging drilling fluids obtained in the examples and comparative examples was investigated by using a plugging evaluation simulation experiment device.
  • the experimental method is: add 3L oil-based plugging drilling fluid into the plugging simulation device to evaluate the plugging ability of wedge-shaped fractures with a fracture width of 5mm ⁇ 4mm. .
  • Table 1 The plugging performance of different oil-based plugging drilling fluids

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Abstract

A coated rubber particle, a preparation method therefor and use thereof as a leakage blocking material in a drilling fluid. The coated rubber particle has a rubber core and a coating layer. The fluorine content (atomic percent) of the core is 0-15%, and the fluorine content (atomic percent) of the coating layer is 30-80%. The oil absorption rate in 24 h of the coated rubber particle is 4% or less. The coated rubber particle has good oil resistance, and is suitable as a leakage blocking material in a drilling fluid, in particular an oil-based drilling fluid.

Description

[根据细则37.2由ISA制定的发明名称]　包覆橡胶颗粒、其制造方法及其应用[Title of invention made by ISA pursuant to Rule 37.2] Coated rubber particles, method for their manufacture and their use 技术领域technical field
本发明涉及钻井技术领域。具体地说，本发明涉及一种包覆橡胶颗粒、其制造方法及其作为堵漏材料在钻井液中的应用。The present invention relates to the technical field of drilling. Specifically, the present invention relates to a coated rubber particle, its manufacturing method and its application as a plugging material in drilling fluid.
背景技术Background technique
近年来，随着油气勘探开发的进行，深井、复杂地层井逐渐增多，而且钻井施工过程中各种复杂事故频发，尤其是井漏问题更加突出。发生漏失井的数量、漏失量、漏失时间均居高不小，而且堵漏效果也不是很理想，不仅造成了巨大的经济损失，也大大延缓了勘探开发的进程。In recent years, with the development of oil and gas exploration and development, the number of deep wells and wells in complex formations has gradually increased, and various complex accidents have occurred frequently in the process of drilling construction, especially the problem of lost circulation. The number of lost wells, the amount of lost wells, and the lost time are all high, and the plugging effect is not ideal, which not only causes huge economic losses, but also greatly delays the process of exploration and development.
目前，常用的堵漏材料按不同机理和功能主要有桥接类堵漏材料、高失水堵漏材料、保护产层的暂堵材料、化学堵漏材料、无机胶凝堵漏材料和软(硬)塞类堵漏材料等几大类。这些堵漏材料的应用在一定程度上大大减小了因井漏造成的损失。At present, the commonly used plugging materials mainly include bridging plugging materials, high water loss plugging materials, temporary plugging materials to protect production layers, chemical leakage plugging materials, inorganic cementing leakage plugging materials and soft (hard) leakage plugging materials according to different mechanisms and functions. ) plug-type plugging materials and other categories. The application of these lost circulation materials greatly reduces the loss caused by lost circulation to a certain extent.
发明内容SUMMARY OF THE INVENTION
本发明的发明人发现，在当前页岩油气的开发过程中通常使用油基钻井液，由于页岩地层特殊的地质构造和岩性发育特征，井漏时常发生，但目前油基钻井液堵漏缺少专门的油基钻井液堵漏材料，仍使用常规水基钻井液堵漏材料，而一些水基钻井液用弹性堵漏材料具有油溶性，在油基钻井液中会发生溶解，不具备承压堵漏性能，无法适用油基钻井液堵漏。本发明的发明人还发现，水基钻井液堵漏材料多为亲水性材料，与油基钻井液配伍性差，容易受到钻井液侵污而影响堵漏效果或者反向影响钻井液性能，导致井下复杂事故。本发明的发明人进一步发现，具有弹塑性的堵漏颗粒通常具有油溶性，即使耐油橡胶，在油基钻井液中长时间浸泡也会发生部分溶解，引起橡胶强度、弹性等性能下降，从而造成无法形成有效的堵漏或钻井过程中引发复漏。由此可见，现有技术缺少强度高、耐油且具有弹塑性能的堵漏产品。本发明基于这些发现而完成。The inventors of the present invention found that oil-based drilling fluids are usually used in the current shale oil and gas development process. Due to the special geological structure and lithological development characteristics of shale formations, lost circulation often occurs. There is a lack of special oil-based drilling fluid plugging materials, and conventional water-based drilling fluid plugging materials are still used. However, some elastic plugging materials for water-based drilling fluids are oil-soluble and will dissolve in oil-based drilling fluids, and do not have the ability to support The performance of pressure plugging is not suitable for oil-based drilling fluid plugging. The inventors of the present invention also found that most of the water-based drilling fluid plugging materials are hydrophilic materials, which have poor compatibility with oil-based drilling fluids, and are easily affected by drilling fluid contamination, which affects the plugging effect or reversely affects the performance of the drilling fluid, resulting in Complicated underground accident. The inventor of the present invention further found that the elastoplasticity plugging particles are usually oil-soluble, and even if oil-resistant rubber is immersed in oil-based drilling fluid for a long time, partial dissolution will occur, resulting in the decline of rubber strength, elasticity and other properties, thereby causing Failure to form effective plugging or re-leakage during drilling. It can be seen that the prior art lacks leakage plugging products with high strength, oil resistance and elastic-plastic properties. The present invention has been completed based on these findings.
具体而言，本发明涉及以下方面的内容。Specifically, the present invention relates to the following aspects.
1.一种包覆橡胶颗粒，具有橡胶内核和包覆层，其中所述内核的氟元素含量(原子％)为0-15％(优选0-8％)，所述包覆层的氟元素含量(原子％)为30-80％(优选40-65％)，并且所述包覆橡胶颗粒的24h吸油率为4％以下(优选3％以下，更优选1.5-2.5％)。1. A coated rubber particle having a rubber inner core and a coating layer, wherein the fluorine element content (atomic %) of the inner core is 0-15% (preferably 0-8%), and the fluorine element of the coating layer is The content (atomic %) is 30-80% (preferably 40-65%), and the 24h oil absorption of the coated rubber particles is 4% or less (preferably 3% or less, more preferably 1.5-2.5%).
2.前述或后述任一方面所述的包覆橡胶颗粒，其中所述包覆层的高价金属含量(原子％)与所述内核的高价金属含量(原子％)之比为1-10(优选1.2-3)，和/或，所述高价金属选自铝、钙、钛、镁、钡和硅中的至少一种(优选选自钙和硅中的至少一种，特别是钙)，和/或，所述包覆层的高价金属含量(原子％)为0.15-0.50％(优选0.20-0.30％)，和/或，所述内核的高价金属含量(原子％)为0.05-0.2％(优选0.10-0.15％)，和/或，所述包覆层的金属碳比A(原子比)为0.003-0.01(优选0.004-0.008)，和/或，所述内核的金属碳比B(原子比)为0.0008-0.003(优选0.001-0.002)，和/或，所述金属碳比A与所述金属碳比B的比例为2-13(优选3-6)，和/或，所述包覆层的氟碳比(原子比)为1-3(优选1.2-1.8)，和/或，所述内核的氟碳比(原子比)为0-0.25(优选0-0.12)。2. The coated rubber particle according to any one of the preceding or following aspects, wherein the ratio of the high-valent metal content (atomic %) of the coating layer to the high-valent metal content (atomic %) of the inner core is 1-10 ( Preferably 1.2-3), and/or, the high-valent metal is selected from at least one of aluminum, calcium, titanium, magnesium, barium and silicon (preferably selected from at least one of calcium and silicon, especially calcium), And/or, the high-valent metal content (atomic %) of the cladding layer is 0.15-0.50% (preferably 0.20-0.30%), and/or the high-valent metal content (atomic %) of the inner core is 0.05-0.2% (preferably 0.10-0.15%), and/or, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.003-0.01 (preferably 0.004-0.008), and/or, the metal-carbon ratio B ( atomic ratio) is 0.0008-0.003 (preferably 0.001-0.002), and/or, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 2-13 (preferably 3-6), and/or, the The fluorocarbon ratio (atomic ratio) of the coating layer is 1-3 (preferably 1.2-1.8), and/or the fluorocarbon ratio (atomic ratio) of the inner core is 0-0.25 (preferably 0-0.12).
3.前述或后述任一方面所述的包覆橡胶颗粒，其中所述橡胶选自天然橡胶、合成橡胶及其复合材料中的至少一种，和/或，所述包覆层包含无机颗粒(优选无机纳米颗粒，特别是选自碳酸钙纳米颗粒、二氧化硅纳米颗粒、氧化铝纳米颗粒和硅铝纳米颗粒中的至少一种)，和/或，所述包覆层包含含氟聚合物(优选氟代聚烯烃，特别是选自四氟乙烯均聚物、四氟乙烯共聚物、偏氟乙烯均聚物、偏氟乙烯共聚物、六氟丙烯均聚物和六氟丙烯共聚物中的至少一种)。3. The coated rubber particles according to any one of the preceding or following aspects, wherein the rubber is selected from at least one of natural rubber, synthetic rubber and composite materials thereof, and/or, the coating layer comprises inorganic particles (preferably inorganic nanoparticles, especially at least one selected from the group consisting of calcium carbonate nanoparticles, silica nanoparticles, alumina nanoparticles and silica alumina nanoparticles), and/or, the coating layer comprises a fluoropolymer (preferably fluoropolyolefins, especially selected from the group consisting of tetrafluoroethylene homopolymers, tetrafluoroethylene copolymers, vinylidene fluoride homopolymers, vinylidene fluoride copolymers, hexafluoropropylene homopolymers and hexafluoropropylene copolymers at least one of them).
4.前述或后述任一方面所述的包覆橡胶颗粒，其中所述无机颗粒与所述内核的重量比为0.01-0.12(优选0.02-0.05)，和/或，所述含氟聚合物与所述内核的重量比为0.015-0.06(优选0.025-0.04)，和/或，所述包覆橡胶颗粒的平均粒度为0.5-20mm(优选1-5mm)，和/或，所述无机颗粒的平均粒度为10-500nm(优选50-300nm或50-200nm)，和/或，所述包覆层的厚度使得与不具有所述包覆层的情况相比，所述包覆橡胶颗粒的24h吸油率降低20％以上(优选降低30％以上，更优选降低35-60％)，优选所述包覆层的厚度为0.05-500微米(优选1-300微米或20-200微米)，和/或，与不具有所述包覆层的情况相比， 所述包覆橡胶颗粒的24h吸油率降低20％以上(优选降低30％以上，更优选降低35-60％)。4. The coated rubber particles according to any one of the preceding or following aspects, wherein the weight ratio of the inorganic particles to the inner core is 0.01-0.12 (preferably 0.02-0.05), and/or, the fluoropolymer The weight ratio to the inner core is 0.015-0.06 (preferably 0.025-0.04), and/or the average particle size of the coated rubber particles is 0.5-20 mm (preferably 1-5 mm), and/or the inorganic particles The average particle size is 10-500nm (preferably 50-300nm or 50-200nm), and/or the thickness of the coating layer is such that the coating rubber particles have a 24h oil absorption rate is reduced by more than 20% (preferably by more than 30%, more preferably by 35-60%), preferably the thickness of the coating layer is 0.05-500 microns (preferably 1-300 microns or 20-200 microns), and /or, compared with the case without the coating layer, the 24-hour oil absorption of the coated rubber particles is reduced by more than 20% (preferably by more than 30%, more preferably by 35-60%).
5.一种包覆橡胶颗粒的制造方法，包括以下步骤：5. A manufacturing method of coated rubber particles, comprising the following steps:
(1)提供橡胶颗粒，和(1) provide rubber pellets, and
(2)用选自无机颗粒和含氟聚合物的至少一者(优选两者)涂覆(优选喷涂或喷淋)所述橡胶颗粒，获得所述包覆橡胶颗粒。(2) Coating (preferably spraying or spraying) the rubber particles with at least one (preferably both) selected from inorganic particles and fluoropolymers to obtain the coated rubber particles.
6.前述或后述任一方面所述的制造方法，其中所述步骤(2)包括：6. The manufacturing method according to any one of the preceding or following aspects, wherein the step (2) comprises:
(2-1)用所述无机颗粒进行所述涂覆(优选喷涂或喷淋)，然后干燥或不干燥(优选不干燥)，和(优选然后)，(2-1) The coating (preferably spraying or spraying) with the inorganic particles, followed by drying or not (preferably not drying), and (preferably then),
(2-2)用所述含氟聚合物进行所述涂覆(优选喷涂或喷淋)，然后干燥或不干燥(优选不干燥)。(2-2) The coating (preferably spraying or showering) is performed with the fluoropolymer, and then dried or not (preferably not dried).
7.前述或后述任一方面所述的制造方法，其中所述含氟聚合物是氟代聚烯烃，特别是选自四氟乙烯均聚物、四氟乙烯共聚物、偏氟乙烯均聚物、偏氟乙烯共聚物、六氟丙烯均聚物和六氟丙烯共聚物中的至少一种，和/或，所述无机颗粒是无机纳米颗粒，特别是选自碳酸钙纳米颗粒、二氧化硅纳米颗粒、氧化铝纳米颗粒和硅铝纳米颗粒中的至少一种，和/或，所述橡胶选自天然橡胶、合成橡胶及其复合材料中的至少一种，和/或，所述橡胶颗粒的平均粒度为0.5-20mm(优选1-5mm)，和/或，所述无机颗粒的平均粒度为10-500nm(优选50-300nm或50-200nm)，和/或，所述橡胶颗粒包括废弃橡胶颗粒。7. The production method according to any one of the preceding or following aspects, wherein the fluoropolymer is a fluoropolyolefin, in particular selected from the group consisting of tetrafluoroethylene homopolymer, tetrafluoroethylene copolymer, vinylidene fluoride homopolymer At least one of compounds, vinylidene fluoride copolymers, hexafluoropropylene homopolymers and hexafluoropropylene copolymers, and/or, the inorganic particles are inorganic nanoparticles, especially selected from calcium carbonate nanoparticles, carbon dioxide At least one of silicon nanoparticles, aluminum oxide nanoparticles and silicon aluminum nanoparticles, and/or, the rubber is selected from at least one of natural rubber, synthetic rubber and composite materials thereof, and/or, the rubber The particles have an average particle size of 0.5-20 mm (preferably 1-5 mm), and/or the inorganic particles have an average particle size of 10-500 nm (preferably 50-300 nm or 50-200 nm), and/or the rubber particles include Waste rubber pellets.
8.前述或后述任一方面所述的制造方法，其中所述无机颗粒以含有所述无机颗粒的涂覆组合物(称为无机涂覆组合物)的形式使用，和/或，所述含氟聚合物以含有所述含氟聚合物的涂覆组合物(称为含氟涂覆组合物)的形式使用。8. The manufacturing method of any one of the preceding or following aspects, wherein the inorganic particles are used in the form of a coating composition containing the inorganic particles (referred to as an inorganic coating composition), and/or, the Fluoropolymers are used in the form of coating compositions containing the fluoropolymers (referred to as fluorocoating compositions).
9.前述或后述任一方面所述的制造方法，其中所述无机涂覆组合物包含所述无机颗粒、粘结剂(优选聚合物乳液，特别是选自聚丙烯酸酯系乳液、聚醋酸乙烯酯系乳液、α-氰基丙烯酸乙酯乳液、环氧树脂乳液、聚氨酯乳液和松香乳胶中的至少一种，更特别是聚醋酸乙烯酯系乳液)、任选的偶联剂(优选硅烷偶联剂，更优选选自乙烯基三C1-6烷氧基(优选三C1-4烷氧基)硅烷中的至少一种，特别是选自乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷和乙烯基三(β-甲氧乙氧基)硅烷中的至少一种)、任选的润湿剂(优选选自聚乙 二醇、烷基硫酸盐、有机磺酸盐和聚氧乙烯醚中的至少一种，更优选选自聚乙二醇和烷基硫酸盐中的至少一种)、任选的分散剂(优选选自聚丙烯酸盐、纤维素衍生物、聚丙烯酰胺和聚氧乙烯醚磷酸酯盐中的至少一种，更优选纤维素硫酸钠)、以及任选的媒介(优选水)，和/或，所述含氟涂覆组合物包含所述含氟聚合物、分散剂(优选表面活性剂，特别是选自全氟辛基磺酸钾和全氟辛酸铵中的至少一种，更优选全氟辛基磺酸钾)和媒介(优选水)。9. The manufacturing method according to any one of the preceding or following aspects, wherein the inorganic coating composition comprises the inorganic particles, a binder (preferably a polymer emulsion, especially a polyacrylate emulsion, polyacetic acid) At least one of vinyl ester emulsion, ethyl α-cyanoacrylate emulsion, epoxy resin emulsion, polyurethane emulsion and rosin emulsion, more particularly polyvinyl acetate emulsion), optional coupling agent (preferably silane Coupling agent, more preferably at least one selected from vinyl tri-C1-6 alkoxy (preferably tri-C1-4 alkoxy) silane, especially selected from vinyl triethoxy silane, vinyl trimethoxy silane at least one of vinyl tris(beta-methoxyethoxy)silane), optional wetting agent (preferably selected from polyethylene glycols, alkyl sulfates, organic sulfonates, and polyoxyethylene glycols) At least one of vinyl ethers, more preferably selected from at least one of polyethylene glycols and alkyl sulfates), optional dispersants (preferably selected from polyacrylates, cellulose derivatives, polyacrylamides and polyacrylamide) at least one of oxyethylene ether phosphate salts, more preferably sodium cellulose sulfate), and an optional vehicle (preferably water), and/or, the fluorine-containing coating composition comprises the fluoropolymer, A dispersant (preferably a surfactant, especially at least one selected from potassium perfluorooctanesulfonate and ammonium perfluorooctanoate, more preferably potassium perfluorooctanesulfonate) and a vehicle (preferably water).
10.前述或后述任一方面所述的制造方法，其中以重量份计，所述无机涂覆组合物包含所述无机颗粒10-50重量份(优选15-25重量份)、所述粘结剂10-30重量份(优选20-30重量份)、所述任选的偶联剂0-10重量份(优选2-5重量份)、所述任选的润湿剂0-10重量份(优选2-5重量份)、所述任选的分散剂0-10重量份(优选2-5重量份)、以及所述任选的媒介0-10重量份(优选2-5重量份)，和/或，以重量份计，所述含氟涂覆组合物包含所述含氟聚合物3-15重量份(优选5-10重量份)、所述分散剂1-8重量份(优选1-3重量份)和所述媒介20-50重量份(优选25-40重量份)。10. The manufacturing method according to any one of the preceding or following aspects, wherein in parts by weight, the inorganic coating composition comprises 10-50 parts by weight (preferably 15-25 parts by weight) of the inorganic particles, the adhesive 10-30 parts by weight (preferably 20-30 parts by weight) of a binding agent, 0-10 parts by weight (preferably 2-5 parts by weight) of the optional coupling agent, 0-10 parts by weight of the optional wetting agent parts (preferably 2-5 parts by weight), 0-10 parts by weight (preferably 2-5 parts by weight) of the optional dispersant, and 0-10 parts by weight (preferably 2-5 parts by weight) of the optional medium ), and/or, in parts by weight, the fluorine-containing coating composition comprises 3-15 parts by weight (preferably 5-10 parts by weight) of the fluoropolymer, 1-8 parts by weight of the dispersant ( Preferably 1-3 parts by weight) and 20-50 parts by weight (preferably 25-40 parts by weight) of the medium.
11.前述或后述任一方面所述的制造方法，其中在所述步骤(1)与所述步骤(2)之间还包括润湿步骤：用润湿剂(优选选自羧酸和醇中的至少一种，更优选选自水易溶性羧酸和水易溶性醇中的至少一种，特别是选自C1-6一元或多元羧酸和C1-6一元或多元醇中的至少一种，更特别是选自乙酸和甘油中的至少一种)对所述橡胶颗粒进行处理(优选通过喷涂或喷淋)，然后干燥或不干燥(优选不干燥)。11. The manufacturing method described in any one of the foregoing or later, wherein between the step (1) and the step (2), a wetting step is also included: using a wetting agent (preferably selected from carboxylic acids and alcohols) At least one in, more preferably selected from at least one in water-soluble carboxylic acid and water-soluble alcohol, especially selected from at least one in C1-6 monobasic or polyvalent carboxylic acid and C1-6 monobasic or polyhydric alcohol. The rubber particles are treated (preferably by spraying or spraying), more particularly at least one selected from the group consisting of acetic acid and glycerol) and then dried or not (preferably not dried).
12.前述或后述任一方面所述的制造方法，其中所述润湿剂以含有所述润湿剂的组合物(称为润湿剂组合物)的形式使用，并且所述润湿剂组合物包含所述润湿剂和水。12. The manufacturing method of any one of the preceding or following aspects, wherein the wetting agent is used in the form of a composition containing the wetting agent (referred to as a wetting agent composition), and the wetting agent The composition includes the humectant and water.
13.前述或后述任一方面所述的制造方法，其中以重量份计，所述润湿剂组合物包含所述润湿剂2-15重量份(优选3-10重量份)和水98-85重量份(优选90-97重量份)，和/或，所述润湿剂与所述橡胶颗粒的重量比为0.01-0.05(优选0.02-0.035)。13. The manufacturing method described in any one of the preceding or following aspects, wherein in parts by weight, the wetting agent composition comprises 2-15 parts by weight (preferably 3-10 parts by weight) of the wetting agent and water 98 -85 parts by weight (preferably 90-97 parts by weight), and/or, the weight ratio of the wetting agent to the rubber particles is 0.01-0.05 (preferably 0.02-0.035).
14.前述或后述任一方面所述的制造方法，其中所述步骤(2-1)的操作条件包括：喷涂或喷淋法，使用超声振动筛，操作温度为40-85℃(优选45-70℃或55-60℃)，超声频率为5-100KHZ(优选10-50KHZ或20-30KHZ)，振动频率为 10-100HZ(优选25-75HZ或45-55HZ)，喷枪气压控制为0.1-0.5MPaG(优选0.2-0.3MPaG)，喷嘴直径为2-20mm(优选5-10mm)，和/或，所述步骤(2-2)的操作条件包括：喷涂或喷淋法，使用振动筛，操作温度为20-45℃(优选30-35℃)，振动频率为10-100HZ(优选25-75HZ或45-55HZ)，喷枪气压控制为0.1-0.5MPaG(优选0.2-0.3MPaG)，喷嘴直径为2-20mm(优选5-10mm)，无超声或超声频率为5-100KHZ(优选10-50KHZ或20-30KHZ)。14. The manufacturing method described in any one of the foregoing or later, wherein the operating conditions of the step (2-1) include: spraying or spraying method, using an ultrasonic vibrating screen, and the operating temperature is 40-85° C. (preferably 45° C.). -70℃ or 55-60℃), the ultrasonic frequency is 5-100KHZ (preferably 10-50KHZ or 20-30KHZ), the vibration frequency is 10-100HZ (preferably 25-75HZ or 45-55HZ), and the air pressure of the spray gun is 0.1- 0.5MPaG (preferably 0.2-0.3MPaG), the diameter of the nozzle is 2-20mm (preferably 5-10mm), and/or, the operating conditions of the step (2-2) include: spraying or spraying method, using a vibrating screen, The operating temperature is 20-45°C (preferably 30-35°C), the vibration frequency is 10-100HZ (preferably 25-75HZ or 45-55HZ), the air pressure of the spray gun is controlled at 0.1-0.5MPaG (preferably 0.2-0.3MPaG), and the diameter of the nozzle is It is 2-20mm (preferably 5-10mm), without ultrasonic or ultrasonic frequency is 5-100KHZ (preferably 10-50KHZ or 20-30KHZ).
15.前述或后述任一方面所述的制造方法，其中所述无机颗粒与所述橡胶颗粒的重量比为0.01-0.12(优选0.02-0.05)，和/或，所述含氟聚合物与所述橡胶颗粒的重量比为0.015-0.06(优选0.025-0.04)。15. The manufacturing method according to any one of the preceding or following aspects, wherein the weight ratio of the inorganic particles to the rubber particles is 0.01-0.12 (preferably 0.02-0.05), and/or, the fluoropolymer and The weight ratio of the rubber particles is 0.015-0.06 (preferably 0.025-0.04).
16.一种钻井液组合物(优选油基钻井液组合物)，包含堵漏材料和基浆(比如选自白油基钻井液基浆、柴油基钻井液基浆和合成基钻井液基浆中的至少一种)，其中所述堵漏材料包含或者是前述或后述任一方面所述的包覆橡胶颗粒或按照前述或后述任一方面所述的制造方法制造的包覆橡胶颗粒。16. A drilling fluid composition (preferably an oil-based drilling fluid composition) comprising a lost circulation material and a base slurry (such as selected from the group consisting of white oil-based drilling fluid base slurry, diesel-based drilling fluid base slurry, and synthetic-based drilling fluid base slurry At least one of the above-mentioned or later), wherein the loss-stopping material comprises or is the coated rubber particles described in any one of the foregoing or later described or the coated rubber particles manufactured according to any one of the foregoing or later described manufacturing methods.
17.前述或后述任一方面所述的钻井液组合物，其中以所述钻井液组合物的总质量为100wt％计，所述包覆橡胶颗粒的质量百分含量为2-12wt％(优选3-8wt％)。17. The drilling fluid composition according to any one of the preceding or following aspects, wherein based on the total mass of the drilling fluid composition being 100 wt %, the mass percentage of the coated rubber particles is 2-12 wt % ( preferably 3-8 wt%).
附图说明Description of drawings
图1是实施例5制造的包覆橡胶颗粒的SEM照片。FIG. 1 is an SEM photograph of the coated rubber particles produced in Example 5. FIG.
图2是实施例5制造的包覆橡胶颗粒的EDS能谱图。FIG. 2 is an EDS spectrum of the coated rubber particles produced in Example 5. FIG.
技术效果technical effect
根据本发明的包覆橡胶颗粒，与现有技术的堵漏材料相比，耐油性能更好，强度更大，在油基钻井液中长时间高温高压浸泡条件下仍具有良好的弹性变形能力和堵漏性能。为此，利用其压力、温度变形性能，可以有效在地层裂缝、孔喉中形成堆积封堵层，从而实现对裂缝漏层的有效封堵。According to the coated rubber particles of the present invention, compared with the leakage plugging materials in the prior art, the oil resistance performance is better, the strength is higher, and the elastic deformation ability and the plugging performance. Therefore, by using its pressure and temperature deformation properties, it is possible to effectively form accumulation plugging layers in formation fractures and pore throats, so as to achieve effective plugging of fractures and leakage layers.
根据本发明的包覆橡胶颗粒，在井底条件下，橡胶内核会发生形变，涂覆在内核表面的包覆层(特别是惰性颗粒)不会发生脱落，会紧紧贴在橡胶内核的表面，从而防止橡胶颗粒内核溶解在油相中。According to the coated rubber particles of the present invention, the rubber core will be deformed under the condition of the bottom hole, and the coating layer (especially the inert particles) coated on the surface of the core will not fall off, and will stick closely to the surface of the rubber core. , thereby preventing the rubber particle core from dissolving in the oil phase.
根据本发明的包覆橡胶颗粒，由于具备包覆层，特别是在包覆层中包含 无机颗粒的情况下，可以大大增强橡胶内核的强度，承压能力更高。The coated rubber particles according to the present invention have a coating layer, especially when the coating layer contains inorganic particles, the strength of the rubber core can be greatly enhanced, and the pressure bearing capacity is higher.
根据本发明的包覆橡胶颗粒，可以在温度或压力条件下发生弹性变形，挤入孔缝承压封堵，而且包覆层可以与地层吸附胶结，提高滞留能力，封堵孔缝效果良好。The coated rubber particles according to the present invention can elastically deform under temperature or pressure conditions, squeeze into the pores and seams for pressure-bearing sealing, and the coating layer can be adsorbed and cemented with the formation to improve the retention capacity, and the sealing effect of pores and seams is good.
具体实施方式Detailed ways
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。The specific embodiments of the present invention will be described in detail below, but it should be noted that the protection scope of the present invention is not limited by these specific embodiments, but is determined by the appended claims.
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本发明所属领域内一般技术人员常理解的相同意思。在有冲突的情况下，包括定义在内，以本说明书为准。All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference in their entirety. Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
当本说明书以“本领域技术人员已知的”或者“本领域常规已知的”或类似用语来描述材料、方法、部件、装置或设备时，该术语表示本说明书包括提出本申请时本领域常规使用的那些，但也包括目前还不常用，但将变成本领域公认为适用于类似目的的那些。When this specification refers to a material, method, component, device or device as "known to those skilled in the art" or "conventionally known in the art" or similar terms, the term indicates that the specification includes the art at the time of filing the application Those that are conventionally used, but also include those that are not commonly used at present, but will become known in the art to be suitable for similar purposes.
此外，本说明书提到的各种范围均包括它们的端点在内，除非另有明确说明。此外，当对量、浓度或其它值或参数给出范围、一个或多个优选范围或很多优选上限值与优选下限值时，应把它理解为具体公开了由任意对任意范围上限值或优选值与任意范围下限值或优选值所形成的所有范围，不论是否一一公开了这些数值对。Furthermore, the various ranges mentioned in this specification are inclusive of their endpoints unless expressly stated otherwise. Furthermore, when a range, one or more preferred ranges, or a number of preferred upper and lower preferred values are given for an amount, concentration or other value or parameter, it should be understood as specifically disclosing the combination of any to any upper range All ranges formed by a value or preferred value and any lower limit of the range or preferred value, whether or not the pairs are disclosed individually.
在本说明书的上下文中，所谓“基本上”指的是允许存在对于本领域技术人员而言可以接受或认为合理的偏差，比如偏差在±10％以内、±5％以内或者±2％以内。In the context of this specification, "substantially" means to allow for deviations that are acceptable or reasonable to those skilled in the art, such as deviations within ±10%, ±5%, or ±2%.
在本说明书的上下文中，SEM照片和EDS能谱的测量条件包括：场发射扫描电子显微镜(日本JEOL，型号JSM-7200F)，10.0KV，放大倍率为5000倍，使用电镜自带能谱扫描仪测试样品表面，自动计算生成并输出质量百分比测量结果。样品在测量前进行充分干燥。测量前，对样品进行切割，在真空镀膜仪中向切割断面喷镀一层导电层，然后将样品用导电双面胶粘附于样 品台上，再送入电镜进行测量。In the context of this specification, the measurement conditions for SEM photos and EDS spectra include: Field Emission Scanning Electron Microscope (JEOL, Japan, model JSM-7200F), 10.0KV, magnification of 5000 times, using the electron microscope with its own energy spectrum scanner Test the surface of the sample, automatically calculate and output the mass percentage measurement results. Samples were thoroughly dried prior to measurement. Before measurement, the sample was cut, and a conductive layer was sprayed on the cut section in a vacuum coater, and then the sample was adhered to the sample table with conductive double-sided tape, and then sent to the electron microscope for measurement.
在本说明书的上下文中，24h吸油率的测试方法包括：将待测样品颗粒在80℃下干燥4小时，称重并记录重量为W1(一般为0.6g左右)。将干燥后的待测样品放入500ml的0号柴油中在60℃下浸泡24h，然后将浸泡后的待测样品取出，并用吸油纸吸净颗粒表面的附着油，称重并记录重量为W2。接着，用公式φ 吸＝(W 2-W 1)/W 1×100％计算24h吸油率Φ 吸。 In the context of this specification, the test method for 24h oil absorption includes: drying the sample particles to be tested at 80°C for 4 hours, weighing and recording the weight as W1 (generally about 0.6g). Put the dried sample to be tested in 500ml of No. 0 diesel oil and soak it at 60°C for 24 hours, then take out the sample to be tested after soaking, and use oil-absorbing paper to absorb the oil attached to the surface of the particles, weigh and record the weight as W2 . Next, the 24-h oil absorption rate Φsuction was calculated using the formula φsuction =(W 2 −W 1 )/W 1 ×100%.
在没有明确指明的情况下，本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的，而且压力是表压。All percentages, parts, ratios, etc. mentioned in this specification are on a weight basis, and pressures are gauge pressures, unless expressly indicated.
在本说明书的上下文中，本发明的任何两个或多个实施方式都可以任意组合，由此而形成的技术方案属于本说明书原始公开内容的一部分，同时也落入本发明的保护范围。In the context of this specification, any two or more embodiments of the present invention can be combined arbitrarily, and the technical solutions formed thereby belong to a part of the original disclosure content of this specification, and also fall within the protection scope of the present invention.
根据本发明的一个实施方式，涉及一种包覆橡胶颗粒，其具有橡胶内核和包覆层。在此，所述包覆橡胶颗粒的耐油性良好，特别适合作为堵漏材料用于钻井液，特别是油基钻井液。According to one embodiment of the present invention, it relates to a coated rubber particle having a rubber core and a coating layer. Here, the coated rubber particles have good oil resistance, and are particularly suitable for use in drilling fluids, especially oil-based drilling fluids, as a plugging material.
根据本发明的一个实施方式，所述内核的氟元素含量(原子％)一般为0-15％，优选0-8％。在此，所述内核的氟元素含量通过SEM和EDS能谱法进行测量。According to an embodiment of the present invention, the fluorine element content (at %) of the inner core is generally 0-15%, preferably 0-8%. Here, the fluorine element content of the inner core was measured by SEM and EDS spectroscopy.
根据本发明的一个实施方式，所述包覆层的氟元素含量(原子％)一般为30-80％，优选40-65％。在此，所述包覆层的氟元素含量通过SEM和EDS能谱法进行测量。According to an embodiment of the present invention, the fluorine element content (atomic %) of the coating layer is generally 30-80%, preferably 40-65%. Here, the fluorine element content of the coating layer was measured by SEM and EDS spectroscopy.
根据本发明的一个实施方式，所述包覆橡胶颗粒的24h吸油率一般为4％以下，优选3％以下，更优选1.5-2.5％。本发明的发明人认为，如此低的24h吸油率是现有技术的封堵材料所无法实现的。According to an embodiment of the present invention, the 24-hour oil absorption of the coated rubber particles is generally below 4%, preferably below 3%, more preferably 1.5-2.5%. The inventors of the present invention believe that such a low 24h oil absorption rate cannot be achieved by the plugging materials in the prior art.
根据本发明的一个实施方式，所述包覆层的高价金属含量(原子％)为0.15-0.50％，优选0.20-0.30％。在此，所述包覆层的高价金属含量通过SEM和EDS能谱法进行测量。According to an embodiment of the present invention, the high-valent metal content (atomic %) of the coating layer is 0.15-0.50%, preferably 0.20-0.30%. Here, the high-valent metal content of the coating layer was measured by SEM and EDS spectroscopy.
根据本发明的一个实施方式，所述内核的高价金属含量(原子％)为0.05-0.2％，优选0.10-0.15％。在此，所述内核的高价金属含量通过SEM和EDS能谱法进行测量。According to one embodiment of the present invention, the high-valent metal content (at %) of the inner core is 0.05-0.2%, preferably 0.10-0.15%. Here, the high-valent metal content of the inner core was measured by SEM and EDS spectroscopy.
根据本发明的一个实施方式，所述高价金属选自铝、钙、钛、镁、钡和 硅中的至少一种，优选选自钙和硅中的至少一种，特别是钙。According to one embodiment of the present invention, the high-valent metal is selected from at least one of aluminum, calcium, titanium, magnesium, barium and silicon, preferably selected from at least one of calcium and silicon, especially calcium.
根据本发明的一个实施方式，所述包覆层的高价金属含量(原子％)与所述内核的高价金属含量(原子％)之比一般为1-10，优选1.2-3。According to an embodiment of the present invention, the ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is generally 1-10, preferably 1.2-3.
根据本发明的一个实施方式，所述包覆层的金属碳比(原子比，称为金属碳比A)为0.003-0.01，优选0.004-0.008。在此，所述包覆层的金属碳比通过SEM和EDS能谱法进行测量。According to an embodiment of the present invention, the metal-to-carbon ratio (atomic ratio, referred to as metal-to-carbon ratio A) of the coating layer is 0.003-0.01, preferably 0.004-0.008. Here, the metal-to-carbon ratio of the cladding layer was measured by SEM and EDS spectroscopy.
根据本发明的一个实施方式，所述内核的金属碳比(原子比，称为金属碳比B)为0.0008-0.003，优选0.001-0.002。在此，所述内核的金属碳比通过SEM和EDS能谱法进行测量。According to an embodiment of the present invention, the metal-to-carbon ratio (atomic ratio, referred to as metal-to-carbon ratio B) of the inner core is 0.0008-0.003, preferably 0.001-0.002. Here, the metal-to-carbon ratio of the inner core was measured by SEM and EDS spectroscopy.
根据本发明的一个实施方式，所述金属碳比A与所述金属碳比B的比例为2-13，优选3-6。According to an embodiment of the present invention, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 2-13, preferably 3-6.
根据本发明的一个实施方式，所述包覆层的氟碳比(原子比)为1-3，优选1.2-1.8。在此，所述包覆层的氟碳比通过SEM和EDS能谱法进行测量。According to an embodiment of the present invention, the fluorocarbon ratio (atomic ratio) of the coating layer is 1-3, preferably 1.2-1.8. Here, the fluorocarbon ratio of the coating layer was measured by SEM and EDS spectroscopy.
根据本发明的一个实施方式，所述内核的氟碳比(原子比)为0-0.25，优选0-0.12。在此，所述内核的氟碳比通过SEM和EDS能谱法进行测量。According to one embodiment of the present invention, the fluorocarbon ratio (atomic ratio) of the inner core is 0-0.25, preferably 0-0.12. Here, the fluorocarbon ratio of the inner core was measured by SEM and EDS spectroscopy.
根据本发明的一个实施方式，所述橡胶选自天然橡胶、合成橡胶及其复合材料中的至少一种。在此，所述橡胶可以是新制橡胶，也可以是废弃橡胶，并且从成本角度考虑，优选后者。According to an embodiment of the present invention, the rubber is selected from at least one of natural rubber, synthetic rubber and composite materials thereof. Here, the rubber may be virgin rubber or waste rubber, and the latter is preferred from the viewpoint of cost.
根据本发明的一个实施方式，所述包覆层包含无机颗粒。在此，作为所述无机颗粒，优选无机纳米颗粒，特别是选自碳酸钙纳米颗粒、二氧化硅纳米颗粒、氧化铝纳米颗粒和硅铝纳米颗粒中的至少一种。According to one embodiment of the present invention, the coating layer comprises inorganic particles. Herein, as the inorganic particles, inorganic nanoparticles are preferred, especially at least one selected from the group consisting of calcium carbonate nanoparticles, silica nanoparticles, alumina nanoparticles, and silicon-alumina nanoparticles.
根据本发明的一个实施方式，所述包覆层包含含氟聚合物。在此，作为所述含氟聚合物，优选氟代聚烯烃，特别是选自四氟乙烯均聚物、四氟乙烯共聚物、偏氟乙烯均聚物、偏氟乙烯共聚物、六氟丙烯均聚物和六氟丙烯共聚物中的至少一种。According to one embodiment of the present invention, the cladding layer comprises a fluoropolymer. Here, as the fluorine-containing polymer, a fluorinated polyolefin is preferable, and is especially selected from the group consisting of tetrafluoroethylene homopolymer, tetrafluoroethylene copolymer, vinylidene fluoride homopolymer, vinylidene fluoride copolymer, hexafluoropropylene At least one of a homopolymer and a hexafluoropropylene copolymer.
根据本发明的一个实施方式，所述无机颗粒与所述内核的重量比为0.01-0.12，优选0.02-0.05。According to an embodiment of the present invention, the weight ratio of the inorganic particles to the inner core is 0.01-0.12, preferably 0.02-0.05.
根据本发明的一个实施方式，所述含氟聚合物与所述内核的重量比为0.015-0.06，优选0.025-0.04。According to one embodiment of the present invention, the weight ratio of the fluoropolymer to the inner core is 0.015-0.06, preferably 0.025-0.04.
根据本发明的一个实施方式，所述包覆橡胶颗粒的平均粒度一般为 0.5-20mm，优选1-5mm。本发明的包覆橡胶颗粒可以是球形、片状、方块状等任意形状，也可以是任意的不规则形状，并没有特别的限定。为此，所述包覆橡胶颗粒的平均粒度一般指的是其长、宽、高之和的平均值，或者是其最大尺寸和最小尺寸的平均值，或者是颗粒的等效直径。According to an embodiment of the present invention, the average particle size of the coated rubber particles is generally 0.5-20 mm, preferably 1-5 mm. The coated rubber particles of the present invention may be in any shape such as spherical, flake, and square, or may be in any irregular shape, and are not particularly limited. To this end, the average particle size of the coated rubber particles generally refers to the average value of the sum of the length, width and height, or the average value of the largest size and the smallest size, or the equivalent diameter of the particles.
根据本发明的一个实施方式，所述无机颗粒的平均粒度为10-500nm，优选50-300nm或50-200nm。在此，所述无机颗粒的平均粒度通过动态光散射纳米颗粒粒度分布测量法进行测量。According to an embodiment of the present invention, the average particle size of the inorganic particles is 10-500 nm, preferably 50-300 nm or 50-200 nm. Here, the average particle size of the inorganic particles is measured by dynamic light scattering nanoparticle size distribution measurement.
根据本发明的一个实施方式，在所述包覆橡胶颗粒中，所述包覆层可以是连续的，即覆盖所述内核的整个表面，也可以是不连续的，即仅覆盖所述内核的一部分，并没有特别的限定。但是，从本发明技术效果更为优异的角度来看，优选是连续的或基本上连续的。According to an embodiment of the present invention, in the coated rubber particles, the coating layer may be continuous, that is, cover the entire surface of the inner core, or discontinuous, that is, only cover the inner core. Some of them are not particularly limited. However, from the viewpoint that the technical effect of the present invention is more excellent, it is preferably continuous or substantially continuous.
根据本发明的一个实施方式，在所述包覆橡胶颗粒中，对所述包覆层的厚度没有特别的限制，只要在本领域技术人员常规理解的范围内构成物质层即可。从本发明技术效果更为优异实现的角度来看，所述包覆层的厚度使得与不具有所述包覆层的情况相比，所述包覆橡胶颗粒的24h吸油率降低20％以上，优选降低30％以上，更优选降低35-60％。作为举例而言，所述包覆层的厚度一般为0.05-500微米，优选1-300微米或20-200微米。在此，所述厚度指的是所述包覆层的平均厚度，其测量方法包括：在SEM照片上选择任意20个点，取平均值即为包覆层平均厚度。According to an embodiment of the present invention, in the coated rubber particles, the thickness of the coating layer is not particularly limited, as long as a substance layer is formed within a range commonly understood by those skilled in the art. From the viewpoint of achieving more excellent technical effects of the present invention, the thickness of the coating layer reduces the 24-hour oil absorption rate of the coated rubber particles by more than 20% compared with the case without the coating layer, A reduction of more than 30% is preferred, and a reduction of 35-60% is more preferred. As an example, the thickness of the coating layer is generally 0.05-500 microns, preferably 1-300 microns or 20-200 microns. Here, the thickness refers to the average thickness of the cladding layer, and the measurement method includes: selecting any 20 points on the SEM photo, and taking the average value is the average thickness of the cladding layer.
根据本发明的一个实施方式，与不具有所述包覆层的情况相比，所述包覆橡胶颗粒的24h吸油率降低20％以上，优选降低30％以上，更优选降低35-60％。According to an embodiment of the present invention, compared with the case without the coating layer, the 24-hour oil absorption rate of the coated rubber particles is reduced by more than 20%, preferably by more than 30%, and more preferably by 35-60%.
根据本发明的一个实施方式，还涉及一种包覆橡胶颗粒的制造方法。所述制造方法可以用于制造本发明的包覆橡胶颗粒。According to one embodiment of the present invention, it also relates to a method for manufacturing coated rubber particles. The manufacturing method can be used to manufacture the coated rubber particles of the present invention.
根据本发明的一个实施方式，所述包覆橡胶颗粒的制造方法包括以下步骤：According to an embodiment of the present invention, the manufacturing method of the coated rubber particles comprises the following steps:
(1)提供橡胶颗粒，和(1) provide rubber pellets, and
(2)用选自无机颗粒和含氟聚合物的至少一者涂覆所述橡胶颗粒，获得所述包覆橡胶颗粒。(2) Coating the rubber particles with at least one selected from inorganic particles and fluorine-containing polymers to obtain the coated rubber particles.
根据本发明的一个实施方式，在所述制造方法中，所述无机颗粒与所述橡胶颗粒的重量比一般为0.01-0.12，优选0.02-0.05。According to an embodiment of the present invention, in the manufacturing method, the weight ratio of the inorganic particles to the rubber particles is generally 0.01-0.12, preferably 0.02-0.05.
根据本发明的一个实施方式，在所述制造方法中，所述含氟聚合物与所述橡胶颗粒的重量比一般为0.015-0.06，优选0.025-0.04。According to an embodiment of the present invention, in the manufacturing method, the weight ratio of the fluoropolymer to the rubber particles is generally 0.015-0.06, preferably 0.025-0.04.
根据本发明的一个实施方式，在所述步骤(2)中，作为涂敷材料，可以使用无机颗粒和含氟聚合物中的一种材料，也可以两种材料均使用，优选两种材料均使用。According to an embodiment of the present invention, in the step (2), as the coating material, one of inorganic particles and fluoropolymer may be used, or both materials may be used, preferably both materials are used. use.
根据本发明的一个实施方式，在所述步骤(2)中，所述涂覆可以按照本领域常规已知的任何方式和方法进行，只要能够实现所述橡胶颗粒表面的涂敷(优选均匀涂敷)即可，但从涂敷均匀性的角度来看，优选喷涂或喷淋。According to an embodiment of the present invention, in the step (2), the coating can be performed in any manner and method conventionally known in the art, as long as the coating (preferably uniform coating) on the surface of the rubber particles can be achieved coating), but from the viewpoint of coating uniformity, spraying or spraying is preferred.
根据本发明的一个实施方式，在所述制造方法中，所述橡胶颗粒选自天然橡胶颗粒、合成橡胶颗粒及其复合材料颗粒中的至少一种。特别地，所述橡胶颗粒包括废弃橡胶颗粒，也即用废弃橡胶制成的颗粒。According to an embodiment of the present invention, in the manufacturing method, the rubber particles are selected from at least one of natural rubber particles, synthetic rubber particles and composite material particles thereof. In particular, the rubber particles include waste rubber particles, ie particles made from waste rubber.
根据本发明的一个实施方式，所述橡胶颗粒在包覆之前的24h吸油率一般为4-6％，而在包覆之后的24h吸油率一般可以降低至4％以下，优选3％以下，更优选降低至1.5-2.5％。According to an embodiment of the present invention, the oil absorption rate of the rubber particles in 24 hours before coating is generally 4-6%, and the oil absorption rate in 24 hours after coating can generally be reduced to below 4%, preferably below 3%, more It is preferably reduced to 1.5-2.5%.
根据本发明的一个实施方式，在所述制造方法中，所述步骤(2)包括步骤(2-1)：用所述无机颗粒进行涂覆，然后干燥或不干燥，优选不干燥。According to an embodiment of the present invention, in the manufacturing method, the step (2) includes a step (2-1): coating with the inorganic particles, and then drying or not drying, preferably not drying.
根据本发明的一个实施方式，在所述步骤(2-1)中，所述涂覆可以按照本领域常规已知的任何方式和方法进行，只要能够实现所述橡胶颗粒表面的涂敷(优选均匀涂敷)即可，但从涂敷均匀性的角度来看，优选喷涂或喷淋。According to an embodiment of the present invention, in the step (2-1), the coating can be performed in any manner and method conventionally known in the art, as long as the coating on the surface of the rubber particles can be achieved (preferably Uniform coating) is sufficient, but from the viewpoint of coating uniformity, spraying or spraying is preferred.
根据本发明的一个实施方式，在所述步骤(2-1)中，从技术效果实现角度出发，优选使用超声振动筛进行。在此，超声频率为5-100KHZ，优选10-50KHZ或20-30KHZ，振动频率为10-100HZ，优选25-75HZ或45-55HZ。According to an embodiment of the present invention, in the step (2-1), from the perspective of technical effect realization, it is preferable to use an ultrasonic vibrating screen. Here, the ultrasonic frequency is 5-100KHZ, preferably 10-50KHZ or 20-30KHZ, and the vibration frequency is 10-100HZ, preferably 25-75HZ or 45-55HZ.
根据本发明的一个实施方式，在所述步骤(2-1)中，操作温度为40-85℃，优选45-70℃或55-60℃。According to an embodiment of the present invention, in the step (2-1), the operating temperature is 40-85°C, preferably 45-70°C or 55-60°C.
根据本发明的一个实施方式，作为所述喷涂或喷淋优选的操作条件，喷枪气压控制为0.1-0.5MPaG，优选0.2-0.3MPaG，喷嘴直径为2-20mm，优选5-10mm。According to an embodiment of the present invention, as the preferred operating conditions for the spraying or spraying, the air pressure of the spray gun is controlled to be 0.1-0.5 MPaG, preferably 0.2-0.3 MPaG, and the diameter of the nozzle is 2-20 mm, preferably 5-10 mm.
根据本发明的一个实施方式，在所述制造方法中，所述步骤(2)包括步骤(2-2)：用所述含氟聚合物进行涂覆，然后干燥或不干燥，优选不干燥。According to an embodiment of the present invention, in the manufacturing method, the step (2) includes a step (2-2): coating with the fluoropolymer, and then drying or not drying, preferably not drying.
根据本发明的一个实施方式，在所述步骤(2-2)中，所述涂覆可以按照 本领域常规已知的任何方式和方法进行，只要能够实现所述橡胶颗粒表面的涂敷(优选均匀涂敷)即可，但从涂敷均匀性的角度来看，优选喷涂或喷淋。According to an embodiment of the present invention, in the step (2-2), the coating can be performed in any manner and method conventionally known in the art, as long as the coating on the surface of the rubber particles can be achieved (preferably Uniform coating) is sufficient, but from the viewpoint of coating uniformity, spraying or spraying is preferred.
根据本发明的一个实施方式，在所述步骤(2-2)中，从技术效果实现角度出发，优选使用振动筛或超声振动筛进行。在此，振动频率一般为10-100HZ，优选25-75HZ或45-55HZ，无超声或者使用超声，此时的超声频率一般为5-100KHZ，优选10-50KHZ或20-30KHZ。According to an embodiment of the present invention, in the step (2-2), from the perspective of technical effect realization, it is preferable to use a vibrating screen or an ultrasonic vibrating screen. Here, the vibration frequency is generally 10-100HZ, preferably 25-75HZ or 45-55HZ, without ultrasound or using ultrasound, the ultrasound frequency at this time is generally 5-100KHZ, preferably 10-50KHZ or 20-30KHZ.
根据本发明的一个实施方式，在所述步骤(2-2)中，操作温度为20-45℃，优选30-35℃。According to an embodiment of the present invention, in the step (2-2), the operating temperature is 20-45°C, preferably 30-35°C.
根据本发明的一个实施方式，在所述步骤(2-2)中，作为所述喷涂或喷淋优选的操作条件，喷枪气压控制为0.1-0.5MPaG，优选0.2-0.3MPaG，喷嘴直径为2-20mm，优选5-10mm。According to an embodiment of the present invention, in the step (2-2), as the preferred operating conditions for the spraying or spraying, the air pressure of the spray gun is controlled to be 0.1-0.5 MPaG, preferably 0.2-0.3 MPaG, and the nozzle diameter is 2 -20mm, preferably 5-10mm.
根据本发明的一个实施方式，所述步骤(2-2)可以在所述步骤(2-1)之前进行，可以与所述步骤(2-1)同时进行，也可以在所述步骤(2-1)之后进行，优选在所述步骤(2-1)之后进行。According to an embodiment of the present invention, the step (2-2) may be performed before the step (2-1), may be performed simultaneously with the step (2-1), or may be performed after the step (2-1). -1), preferably after the step (2-1).
根据本发明的一个实施方式，在所述制造方法中，所述含氟聚合物是氟代聚烯烃，特别是选自四氟乙烯均聚物、四氟乙烯共聚物、偏氟乙烯均聚物、偏氟乙烯共聚物、六氟丙烯均聚物和六氟丙烯共聚物中的至少一种。According to one embodiment of the present invention, in the manufacturing method, the fluoropolymer is a fluoropolyolefin, in particular selected from the group consisting of tetrafluoroethylene homopolymer, tetrafluoroethylene copolymer, vinylidene fluoride homopolymer , at least one of vinylidene fluoride copolymer, hexafluoropropylene homopolymer and hexafluoropropylene copolymer.
根据本发明的一个实施方式，在所述制造方法中，所述无机颗粒是无机纳米颗粒，特别是选自碳酸钙纳米颗粒、二氧化硅纳米颗粒、氧化铝纳米颗粒和硅铝纳米颗粒中的至少一种。According to an embodiment of the present invention, in the manufacturing method, the inorganic particles are inorganic nanoparticles, in particular selected from calcium carbonate nanoparticles, silica nanoparticles, alumina nanoparticles and silicon aluminum nanoparticles at least one.
根据本发明的一个实施方式，在所述制造方法中，所述橡胶颗粒的平均粒度一般为0.5-20mm，优选1-5mm。在此，所述橡胶颗粒可以是球形、片状、方块状等任意形状，也可以是任意的不规则形状，并没有特别的限定。为此，所述橡胶颗粒的平均粒度一般指的是其长、宽、高之和的平均值，或者是其最大尺寸和最小尺寸的平均值，或者是颗粒的等效直径。According to an embodiment of the present invention, in the manufacturing method, the average particle size of the rubber particles is generally 0.5-20 mm, preferably 1-5 mm. Here, the rubber particles may be in any shape such as spherical, flake, and square, or may be in any irregular shape, and are not particularly limited. To this end, the average particle size of the rubber particles generally refers to the average value of the sum of their length, width and height, or the average value of their largest and smallest dimensions, or the equivalent diameter of the particles.
根据本发明的一个实施方式，在所述制造方法中，所述无机颗粒的平均粒度为10-500nm，优选50-300nm或50-200nm。在此，所述无机颗粒的平均粒度通过动态光散射纳米颗粒粒度分布测量法进行测量。According to an embodiment of the present invention, in the manufacturing method, the average particle size of the inorganic particles is 10-500 nm, preferably 50-300 nm or 50-200 nm. Here, the average particle size of the inorganic particles is measured by dynamic light scattering nanoparticle size distribution measurement.
根据本发明的一个实施方式，在所述制造方法中，所述无机颗粒以含有所述无机颗粒的涂覆组合物(称为无机涂覆组合物)的形式使用。为此，所 述无机涂覆组合物一般包含所述无机颗粒、粘结剂、任选的偶联剂、任选的润湿剂、任选的分散剂、以及任选的媒介。According to an embodiment of the present invention, in the manufacturing method, the inorganic particles are used in the form of a coating composition (referred to as an inorganic coating composition) containing the inorganic particles. To this end, the inorganic coating composition generally comprises the inorganic particles, a binder, an optional coupling agent, an optional wetting agent, an optional dispersing agent, and an optional vehicle.
根据本发明的一个实施方式，对所述粘结剂没有特别的限定，可以使用本领域常规已知的那些。作为所述粘结剂，具体比如可以举出聚合物乳液，特别是选自聚丙烯酸酯系乳液、聚醋酸乙烯酯系乳液、α-氰基丙烯酸乙酯乳液、环氧树脂乳液、聚氨酯乳液和松香乳胶中的至少一种，更特别是聚醋酸乙烯酯系乳液。According to an embodiment of the present invention, the binder is not particularly limited, and those conventionally known in the art may be used. Specific examples of the binder include polymer emulsions, especially selected from polyacrylate emulsions, polyvinyl acetate emulsions, α-cyanoacrylate ethyl ester emulsions, epoxy resin emulsions, polyurethane emulsions and At least one of rosin latex, more particularly polyvinyl acetate based latex.
根据本发明的一个实施方式，对所述偶联剂没有特别的限定，可以使用本领域常规已知的那些。作为所述偶联剂，具体比如可以举出硅烷偶联剂，优选选自乙烯基三C1-6烷氧基(优选三C1-4烷氧基)硅烷中的至少一种，特别是选自乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷和乙烯基三(β-甲氧乙氧基)硅烷中的至少一种。According to an embodiment of the present invention, the coupling agent is not particularly limited, and those conventionally known in the art can be used. Specific examples of the coupling agent include silane coupling agents, preferably at least one selected from vinyltri-C1-6 alkoxy (preferably tri-C1-4 alkoxy) silanes, especially selected from At least one of vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris(beta-methoxyethoxy)silane.
根据本发明的一个实施方式，对所述润湿剂没有特别的限定，可以使用本领域常规已知的那些。作为所述润湿剂，具体比如可以举出选自聚乙二醇、烷基硫酸盐、有机磺酸盐和聚氧乙烯醚中的至少一种，更优选选自聚乙二醇和烷基硫酸盐中的至少一种。According to one embodiment of the present invention, the wetting agent is not particularly limited, and those conventionally known in the art can be used. Specific examples of the wetting agent include at least one selected from polyethylene glycols, alkyl sulfates, organic sulfonates and polyoxyethylene ethers, more preferably polyethylene glycols and alkyl sulfates at least one of the salts.
根据本发明的一个实施方式，对所述分散剂没有特别的限定，可以使用本领域常规已知的那些。作为所述分散剂，具体比如可以举出选自聚丙烯酸盐、纤维素衍生物、聚丙烯酰胺和聚氧乙烯醚磷酸酯盐中的至少一种，更优选纤维素硫酸钠。According to one embodiment of the present invention, the dispersing agent is not particularly limited, and those conventionally known in the art may be used. Specific examples of the dispersing agent include at least one selected from the group consisting of polyacrylates, cellulose derivatives, polyacrylamides, and polyoxyethylene ether phosphates, and more preferably, sodium cellulose sulfate.
根据本发明的一个实施方式，对所述媒介没有特别的限定，可以使用本领域常规已知的那些。作为所述媒介，具体比如可以举出水。According to an embodiment of the present invention, the medium is not particularly limited, and those conventionally known in the art can be used. Specific examples of the medium include water.
根据本发明的一个实施方式，在所述制造方法中，以重量份计，所述无机涂覆组合物包含所述无机颗粒10-50重量份(优选15-25重量份)、所述粘结剂10-30重量份(优选20-30重量份)、所述任选的偶联剂0-10重量份(优选2-5重量份)、所述任选的润湿剂0-10重量份(优选2-5重量份)、所述任选的分散剂0-10重量份(优选2-5重量份)、以及所述任选的媒介0-10重量份(优选2-5重量份)。According to an embodiment of the present invention, in the manufacturing method, in parts by weight, the inorganic coating composition comprises 10-50 parts by weight (preferably 15-25 parts by weight) of the inorganic particles, the adhesive 10-30 parts by weight (preferably 20-30 parts by weight) of the optional coupling agent, 0-10 parts by weight (preferably 2-5 parts by weight) of the optional coupling agent, 0-10 parts by weight of the optional wetting agent (preferably 2-5 parts by weight), 0-10 parts by weight (preferably 2-5 parts by weight) of the optional dispersant, and 0-10 parts by weight (preferably 2-5 parts by weight) of the optional medium .
根据本发明的一个实施方式，在所述制造方法中，所述含氟聚合物以含有所述含氟聚合物的涂覆组合物(称为含氟涂覆组合物)的形式使用。According to one embodiment of the present invention, in the manufacturing method, the fluoropolymer is used in the form of a coating composition containing the fluoropolymer (referred to as a fluorine-containing coating composition).
根据本发明的一个实施方式，在所述制造方法中，所述含氟涂覆组合物至少包含所述含氟聚合物、分散剂和媒介。在此，作为所述媒介，具体比如可以举出水。According to one embodiment of the present invention, in the manufacturing method, the fluorine-containing coating composition includes at least the fluorine-containing polymer, a dispersant and a vehicle. Here, specific examples of the medium include water.
根据本发明的一个实施方式，在所述含氟涂覆组合物中，对所述分散剂没有特别的限定，可以使用本领域常规已知的那些。作为所述分散剂，具体比如可以举出表面活性剂，特别是选自全氟辛基磺酸钾和全氟辛酸铵中的至少一种，更优选全氟辛基磺酸钾。According to an embodiment of the present invention, in the fluorine-containing coating composition, the dispersant is not particularly limited, and those conventionally known in the art can be used. Specific examples of the dispersing agent include surfactants, particularly at least one selected from potassium perfluorooctanesulfonate and ammonium perfluorooctanoate, and potassium perfluorooctanesulfonate is more preferred.
根据本发明的一个实施方式，在所述制造方法中，以重量份计，所述含氟涂覆组合物包含所述含氟聚合物3-15重量份(优选5-10重量份)、所述分散剂1-8重量份(优选1-3重量份)和所述媒介20-50重量份(优选25-40重量份)。According to an embodiment of the present invention, in the manufacturing method, in parts by weight, the fluorine-containing coating composition comprises 3-15 parts by weight (preferably 5-10 parts by weight) of the fluoropolymer, the 1-8 parts by weight (preferably 1-3 parts by weight) of the dispersant and 20-50 parts by weight (preferably 25-40 parts by weight) of the medium.
根据本发明的一个实施方式，在所述制造方法中，在所述步骤(1)与所述步骤(2)之间还包括润湿步骤。根据所述润湿步骤，用润湿剂对所述橡胶颗粒进行处理，然后干燥或不干燥，优选不干燥。According to an embodiment of the present invention, in the manufacturing method, a wetting step is further included between the step (1) and the step (2). According to the wetting step, the rubber particles are treated with a wetting agent and then dried or not, preferably not dried.
根据本发明的一个实施方式，在所述制造方法中，所述润湿剂与所述橡胶颗粒的重量比为0.01-0.05，优选0.02-0.035。According to an embodiment of the present invention, in the manufacturing method, the weight ratio of the wetting agent to the rubber particles is 0.01-0.05, preferably 0.02-0.035.
根据本发明的一个实施方式，在所述润湿步骤中，所述处理可以按照本领域常规已知的任何方式和方法进行，只要能够实现所述橡胶颗粒表面的涂敷(优选均匀涂敷)即可，但从涂敷均匀性的角度来看，优选喷涂或喷淋。According to an embodiment of the present invention, in the wetting step, the treatment may be performed in any manner and method conventionally known in the art, as long as the coating (preferably uniform coating) of the surface of the rubber particles can be achieved. Any, but from the viewpoint of coating uniformity, spraying or showering is preferable.
根据本发明的一个实施方式，在所述润湿步骤中，作为所述润湿剂，比如可以举出选自羧酸和醇中的至少一种，更优选选自水易溶性羧酸和水易溶性醇中的至少一种，特别是选自C1-6一元或多元羧酸和C1-6一元或多元醇中的至少一种，更特别是选自乙酸和甘油中的至少一种。According to an embodiment of the present invention, in the wetting step, as the wetting agent, for example, at least one selected from carboxylic acids and alcohols can be cited, more preferably selected from water-soluble carboxylic acids and water At least one of readily soluble alcohols, in particular at least one selected from C1-6 mono- or polycarboxylic acids and C1-6 mono- or polyhydric alcohols, more particularly at least one selected from acetic acid and glycerol.
根据本发明的一个实施方式，在所述润湿步骤中，所述润湿剂以含有所述润湿剂的组合物(称为润湿剂组合物)的形式使用。在此，所述润湿剂组合物一般包含所述润湿剂和水。According to one embodiment of the present invention, in the wetting step, the wetting agent is used in the form of a composition containing the wetting agent (referred to as a wetting agent composition). Here, the humectant composition generally comprises the humectant and water.
根据本发明的一个实施方式，以重量份计，所述润湿剂组合物包含所述润湿剂2-15重量份(优选3-10重量份)和水98-85重量份(优选90-97重量份)。According to an embodiment of the present invention, in parts by weight, the wetting agent composition comprises 2-15 parts by weight (preferably 3-10 parts by weight) of the wetting agent and 98-85 parts by weight (preferably 90-10 parts by weight) of water 97 parts by weight).
根据本发明的一个优选实施方式，所述包覆橡胶颗粒的制造方法包括：(1)将橡胶颗粒清洗干净、烘干；(2)先后用质量分数为8％的乙酸溶液和5％的丙三醇溶液喷淋橡胶颗粒，喷淋过程中不断翻动橡胶颗粒，确保所有橡 胶颗粒表面充分润湿；(3)将润湿后的橡胶颗粒置于温控型超声振动筛上，筛布孔眼小于橡胶颗粒直径以防其过筛；(4)将质量分数20-30％的无机纳米颗粒加入到含有2-5％硅烷偶联剂的聚醋酸乙烯乳液中，充分搅拌混合而获得无机纳米颗粒分散液；(5)打开超声振动筛，控制温度在55-60℃之间，控制超声频率在20-30KHZ之间，振动频率在50HZ，用喷枪将该无机纳米颗粒分散液均匀喷淋到橡胶颗粒上，喷枪气压控制在0.2-0.3MPa，喷嘴直径控制在5-10mm；(6)喷淋均匀后，继续用质量分数为10-20％的聚四氟乙烯乳液进行喷淋，喷淋过程中保持振动、关闭超声，喷淋结束后调节温度至30-35℃；(7)自然冷却至室温即可得到所述包覆橡胶颗粒。According to a preferred embodiment of the present invention, the manufacturing method of the coated rubber particles includes: (1) cleaning and drying the rubber particles; (2) successively using an acetic acid solution with a mass fraction of 8% and a acrylic acid solution with a mass fraction of 5% The triol solution sprays the rubber particles, and the rubber particles are constantly turned during the spraying process to ensure that the surface of all the rubber particles is fully wetted; (3) The wetted rubber particles are placed on a temperature-controlled ultrasonic vibrating screen, and the screen mesh is smaller than (4) Add 20-30% inorganic nanoparticles by mass fraction to the polyvinyl acetate emulsion containing 2-5% silane coupling agent, stir and mix thoroughly to obtain inorganic nanoparticles dispersed (5) Open the ultrasonic vibrating screen, control the temperature between 55-60°C, control the ultrasonic frequency between 20-30KHZ, and the vibration frequency at 50HZ, and spray the inorganic nanoparticle dispersion liquid evenly on the rubber particles with a spray gun On, the air pressure of the spray gun is controlled at 0.2-0.3MPa, and the diameter of the nozzle is controlled at 5-10mm; (6) After the spray is uniform, continue to spray with a mass fraction of 10-20% polytetrafluoroethylene emulsion. During the spraying process Keep vibrating, turn off ultrasonic waves, and adjust the temperature to 30-35° C. after spraying; (7) Naturally cool to room temperature to obtain the coated rubber particles.
根据本发明的一个实施方式，还涉及一种钻井液组合物，其包含堵漏材料和基浆。在此，所述堵漏材料包含或者是本说明书前文或后文任一实施方式所述的包覆橡胶颗粒，或者，所述堵漏材料包含或者是通过本说明书前文或后文任一实施方式所述的制造方法制造的包覆橡胶颗粒。另外，作为所述钻井液组合物，优选油基钻井液组合物。According to one embodiment of the present invention, it also relates to a drilling fluid composition, which comprises a lost circulation material and a base slurry. Here, the loss-stopping material includes or is the coated rubber particles described in any of the previous or later embodiments of this specification, or, the leakage-stopping material includes or is any of the foregoing or later embodiments of this specification. The coated rubber particles manufactured by the manufacturing method. In addition, as the drilling fluid composition, an oil-based drilling fluid composition is preferable.
根据本发明的一个实施方式，作为所述钻井液基浆，可以使用本领域在钻井液组合物中常规使用的任何基浆，并没有特别的限定，但优选油基钻井液基浆，更具体比如可以举出选自白油基钻井液基浆、柴油基钻井液基浆、合成基钻井液基浆中的至少一种。According to an embodiment of the present invention, as the drilling fluid base slurry, any base slurry conventionally used in drilling fluid compositions in the art can be used, and there is no particular limitation, but oil-based drilling fluid base slurry is preferred, and more specifically For example, at least one selected from the group consisting of white oil-based drilling fluid-based slurry, diesel-based drilling-fluid-based slurry, and synthetic-based drilling fluid-based slurry.
根据本发明的一个实施方式，以所述钻井液组合物的总质量为100wt％计，所述包覆橡胶颗粒的质量百分含量为2-12wt％，优选3-8wt％。According to an embodiment of the present invention, based on the total mass of the drilling fluid composition being 100 wt %, the mass percentage of the coated rubber particles is 2-12 wt %, preferably 3-8 wt %.
根据本发明的一个实施方式，所述钻井液组合物还可以包括本领域在钻井液组合物中常规添加的其他成分，并没有特别的限定。According to an embodiment of the present invention, the drilling fluid composition may further include other components conventionally added in the drilling fluid composition in the art, and is not particularly limited.
实施例Example
以下将通过实施例和对比例对本发明进行进一步的详细描述，但本发明不限于以下实施例。The present invention will be further described in detail below through examples and comparative examples, but the present invention is not limited to the following examples.
在以下的实施例和对比例中，纤维状材料是竹纤维(直径为0.1-0.2mm，长度为3-10mm)，橡胶颗粒A是天然橡胶颗粒(平均粒度为1-3mm)，橡胶颗粒B是丁苯橡胶颗粒(平均粒度为3-5mm)，油基钻井液的组成是柴油+25％盐水+3％乳化剂+2％润湿剂+1％氧化钙+2％氧化沥青。In the following examples and comparative examples, the fibrous material is bamboo fiber (0.1-0.2 mm in diameter, 3-10 mm in length), the rubber particles A are natural rubber particles (average particle size is 1-3 mm), and the rubber particles B are It is styrene-butadiene rubber particles (average particle size is 3-5mm). The composition of oil-based drilling fluid is diesel oil + 25% brine + 3% emulsifier + 2% wetting agent + 1% calcium oxide + 2% oxidized asphalt.
实施例1Example 1
选取1-3mm天然橡胶颗粒A，洗净、烘干；用质量分数为5％的乙酸溶液喷淋、润湿；无机涂覆组合物按重量份计，包含D90为75nm的碳酸钙纳米颗粒15份、聚丙烯酸酯系乳液20份、乙烯基三乙氧基硅烷2份、聚乙二醇2份、聚丙烯酸盐2份、以及水2份，涂覆操作条件为使用超声振动筛，操作温度为40℃，超声频率为10KHZ，振动频率为20HZ，喷枪气压控制为0.1MPaG，喷嘴直径为20mm；含氟涂覆组合物按重量份计，包含四氟乙烯均聚物3份、全氟辛基磺酸钾1份和水20份，涂覆操作条件为使用振动筛，操作温度为30℃，振动频率为40HZ，喷枪气压控制为0.1MPaG，喷嘴直径为20mm，超声频率为20KHZ。Select 1-3mm natural rubber particles A, wash, dry; spray and wet with acetic acid solution with a mass fraction of 5%; the inorganic coating composition, by weight, comprises calcium carbonate nanoparticles with D90 of 75nm 15 parts, 20 parts of polyacrylate emulsion, 2 parts of vinyltriethoxysilane, 2 parts of polyethylene glycol, 2 parts of polyacrylate, and 2 parts of water, the coating operating conditions are the use of ultrasonic vibrating screen, the operating temperature is 40°C, the ultrasonic frequency is 10KHZ, the vibration frequency is 20HZ, the air pressure of the spray gun is controlled at 0.1MPaG, and the diameter of the nozzle is 20mm; the fluorine-containing coating composition, in parts by weight, comprises 3 parts of tetrafluoroethylene homopolymer, 3 parts of perfluorooctane 1 part of potassium sulfonate and 20 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 30°C, the vibration frequency is 40HZ, the air pressure of the spray gun is controlled to 0.1MPaG, the nozzle diameter is 20mm, and the ultrasonic frequency is 20KHZ.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为2.33mm，包覆层的厚度为236.3微米，内核的氟元素含量(原子％)为0％，包覆层的氟元素含量(原子％)为53.5％，包覆橡胶颗粒的24h吸油率为3.2％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为3.6，包覆层的高价金属含量(原子％)为0.18％，内核的高价金属含量(原子％)为0.05％，包覆层的金属碳比A(原子比)为0.004，内核的金属碳比B(原子比)为0.001，金属碳比A与所述金属碳比B的比例为4，包覆层的氟碳比(原子比)为1.20，内核的氟碳比(原子比)为0。The obtained coated rubber particles were analyzed and tested, and the average particle size was 2.33 mm, the thickness of the coating layer was 236.3 microns, the fluorine element content (atomic %) of the inner core was 0%, and the fluorine element content (atomic %) of the coating layer was 0%. %) was 53.5%, and the 24h oil absorption rate of the coated rubber particles was 3.2%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 3.6, the high-valent metal content (atomic %) of the cladding layer is 0.18%, and the high-valent metal content (atomic %) of the inner core is 0.05%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.004, the metal-carbon ratio B (atomic ratio) of the inner core is 0.001, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 4, the cladding The fluorocarbon ratio (atomic ratio) of the layer was 1.20, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.
实施例2Example 2
选取1-3mm合成橡胶颗粒B，洗净、烘干；用质量分数为6％的乙二醇溶液喷淋、润湿；无机涂覆组合物按重量份计，包含D90为75nm的碳酸钙纳米颗粒18份、聚醋酸乙烯酯系乳液25份、乙烯基三甲氧基硅烷4份、烷基硫酸盐3份、纤维素衍生物4份、以及水5份，涂覆操作条件为使用超声振动筛，操作温度为50℃，超声频率为30KHZ，振动频率为30HZ，喷枪气压控制为0.5MPaG，喷嘴直径为5mm；含氟涂覆组合物按重量份计，包含四氟乙烯共聚物6份、全氟辛基磺酸钾2份和水30份，涂覆操作条件为使用振动筛，操作温度为40℃，振动频率为50HZ，喷枪气压控制为0.5MPaG，喷嘴直径为5mm，无超声。Select 1-3mm synthetic rubber particles B, wash, dry; spray and wet with a 6% ethylene glycol solution by weight; the inorganic coating composition, in parts by weight, comprises calcium carbonate nanoparticles with a D90 of 75nm 18 parts of particles, 25 parts of polyvinyl acetate emulsion, 4 parts of vinyltrimethoxysilane, 3 parts of alkyl sulfate, 4 parts of cellulose derivatives, and 5 parts of water, and the coating operation condition is to use an ultrasonic vibrating screen , the operating temperature is 50°C, the ultrasonic frequency is 30KHZ, the vibration frequency is 30HZ, the air pressure of the spray gun is 0.5MPaG, and the diameter of the nozzle is 5mm; 2 parts of potassium fluorooctane sulfonate and 30 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 40 ° C, the vibration frequency is 50 Hz, the air pressure of the spray gun is controlled to 0.5 MPaG, the diameter of the nozzle is 5 mm, and there is no ultrasound.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为2.56mm，包覆层的厚度为349.7微米，内核的氟元素含量(原子％)为1.5％，包覆层的氟元素含量 (原子％)为60.7％，包覆橡胶颗粒的24h吸油率为2.8％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为3，包覆层的高价金属含量(原子％)为0.24％，内核的高价金属含量(原子％)为0.08％，包覆层的金属碳比A(原子比)为0.0063，内核的金属碳比B(原子比)为0.0016，金属碳比A与所述金属碳比B的比例为3.94，包覆层的氟碳比(原子比)为1.60，内核的氟碳比(原子比)为0.03。The obtained coated rubber particles were analyzed and tested, and the average particle size was 2.56 mm, the thickness of the coating layer was 349.7 microns, the fluorine element content (atomic %) of the inner core was 1.5%, and the fluorine element content (atomic %) of the coating layer was 1.5%. %) was 60.7%, and the 24h oil absorption rate of the coated rubber particles was 2.8%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 3, the high-valent metal content (atomic %) of the cladding layer is 0.24%, and the high-valent metal content (atomic %) of the inner core is 0.24% is 0.08%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0063, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0016, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.94. The fluorocarbon ratio (atomic ratio) of the layer was 1.60, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.03.
实施例3Example 3
选取1-3mm合成橡胶颗粒B，洗净、烘干；用质量分数为10％的乙醇溶液喷淋、润湿；无机涂覆组合物按重量份计，包含D90为136nm的二氧化硅纳米颗粒15份、聚丙烯酸酯系乳液20份、乙烯基三甲氧基硅烷2份、聚氧乙烯醚3份、聚丙烯酰胺1份、以及水4份，涂覆操作条件为使用超声振动筛，操作温度为60℃，超声频率为50KHZ，振动频率为75HZ，喷枪气压控制为0.2MPaG，喷嘴直径为10mm；含氟涂覆组合物按重量份计，包含四氟乙烯共聚物12份、全氟辛酸铵2份和水30份，涂覆操作条件为使用振动筛，操作温度为40℃，振动频率为50HZ，喷枪气压控制为0.2MPaG，喷嘴直径为10mm，超声频率为200KHZ。Select 1-3mm synthetic rubber particles B, wash and dry; spray and wet with 10% ethanol solution by weight; the inorganic coating composition, in parts by weight, contains silica nanoparticles with D90 of 136nm 15 parts, 20 parts of polyacrylate emulsion, 2 parts of vinyltrimethoxysilane, 3 parts of polyoxyethylene ether, 1 part of polyacrylamide, and 4 parts of water, the coating operating conditions are the use of ultrasonic vibrating screen, the operating temperature is 60°C, the ultrasonic frequency is 50KHZ, the vibration frequency is 75HZ, the air pressure of the spray gun is controlled at 0.2MPaG, and the diameter of the nozzle is 10mm; the fluorine-containing coating composition, by weight, comprises 12 parts of tetrafluoroethylene copolymer and 2 parts of ammonium perfluorooctanoate And 30 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 40°C, the vibration frequency is 50HZ, the air pressure control of the spray gun is 0.2MPaG, the nozzle diameter is 10mm, and the ultrasonic frequency is 200KHZ.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为2.38mm，包覆层的厚度为193.7微米，内核的氟元素含量(原子％)为4.2％，包覆层的氟元素含量(原子％)为68.1％，包覆橡胶颗粒的24h吸油率为1.8％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为3.6，包覆层的高价金属含量(原子％)为0.26％，内核的高价金属含量(原子％)为0.08％，包覆层的金属碳比A(原子比)为0.0092，内核的金属碳比B(原子比)为0.0029，金属碳比A与所述金属碳比B的比例为3.17，包覆层的氟碳比(原子比)为2.4，内核的氟碳比(原子比)为0.15。The obtained coated rubber particles were analyzed and tested, and the average particle size was 2.38 mm, the thickness of the coating layer was 193.7 microns, the fluorine element content (atomic %) of the inner core was 4.2%, and the fluorine element content (atomic %) of the coating layer was 4.2%. %) was 68.1%, and the 24h oil absorption rate of the coated rubber particles was 1.8%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 3.6, the high-valent metal content (atomic %) of the cladding layer is 0.26%, and the high-valent metal content (atomic %) of the inner core is 0.26% is 0.08%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0092, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0029, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.17, the cladding The fluorocarbon ratio (atomic ratio) of the layer was 2.4, and the fluorocarbon ratio (atomic ratio) of the core was 0.15.
实施例4Example 4
选取3-5mm合成橡胶颗粒B，洗净、烘干；用质量分数为10％的丙三醇溶液喷淋、润湿；无机涂覆组合物按重量份计，包含D90为136nm二氧化硅纳米颗粒25份、环氧树脂乳液25份、乙烯基三(β-甲基乙氧基)硅烷10份、有机磺酸盐2份、聚氧乙烯醚磷酸酯盐2份、以及水5份，涂覆操作条件为使用超声振 动筛，操作温度为60℃，超声频率为50KHZ，振动频率为60HZ，喷枪气压控制为0.3MPaG，喷嘴直径为8mm；含氟涂覆组合物按重量份计，包含六氟丙烯均聚物10份、全氟辛酸铵5份和水30份，涂覆操作条件为使用振动筛，操作温度为35℃，振动频率为55HZ，喷枪气压控制为0.3MPaG，喷嘴直径为8mm，超声频率为50KHZ。Select 3-5mm synthetic rubber particles B, wash, dry; spray and wet with a glycerin solution with a mass fraction of 10%; the inorganic coating composition, in parts by weight, contains D90 of 136nm silicon dioxide nanometers 25 parts of particles, 25 parts of epoxy resin emulsion, 10 parts of vinyl tris(β-methylethoxy) silane, 2 parts of organic sulfonate, 2 parts of polyoxyethylene ether phosphate, and 5 parts of water, coated with The coating operating conditions are to use an ultrasonic vibrating screen, the operating temperature is 60 ℃, the ultrasonic frequency is 50KHZ, the vibration frequency is 60HZ, the air pressure of the spray gun is controlled to be 0.3MPaG, and the diameter of the nozzle is 8mm; 10 parts of fluoropropylene homopolymer, 5 parts of ammonium perfluorooctanoate and 30 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 35°C, the vibration frequency is 55HZ, the air pressure of the spray gun is 0.3MPaG, the diameter of the nozzle is 8mm, and the ultrasonic The frequency is 50KHZ.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为4.67mm，包覆层的厚度为138.3微米，内核的氟元素含量(原子％)为11.5％，包覆层的氟元素含量(原子％)为67.5％，包覆橡胶颗粒的24h吸油率为2.3％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为2.31，包覆层的高价金属含量(原子％)为0.30％，内核的高价金属含量(原子％)为0.12％，包覆层的金属碳比A(原子比)为0.0098，内核的金属碳比B(原子比)为0.0025，金属碳比A与所述金属碳比B的比例为3.92，包覆层的氟碳比(原子比)为2.2，内核的氟碳比(原子比)为0.24。The obtained coated rubber particles were analyzed and tested, and the average particle size was 4.67 mm, the thickness of the coating layer was 138.3 microns, the fluorine element content (atomic %) of the inner core was 11.5%, and the fluorine element content (atomic %) of the coating layer was 11.5%. %) was 67.5%, and the 24h oil absorption rate of the coated rubber particles was 2.3%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2.31, the high-valent metal content (atomic %) of the cladding layer is 0.30%, and the high-valent metal content (atomic %) of the inner core is 0.12%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0098, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0025, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.92. The fluorocarbon ratio (atomic ratio) of the layer was 2.2, and the fluorocarbon ratio (atomic ratio) of the core was 0.24.
实施例5Example 5
选取3-5mm合成橡胶颗粒B，洗净、烘干；用质量分数为12％的乙二酸溶液喷淋、润湿；无机涂覆组合物按重量份计，包含D90为185nm的氧化铝纳米颗粒15份、聚氨酯乳液15份、乙烯基三甲氧基硅烷4份、聚氧乙烯醚6份、纤维素衍生物6份、以及水6份，涂覆操作条件为使用超声振动筛，操作温度为85℃，超声频率为100KHZ，振动频率为80HZ，喷枪气压控制为0.4MPaG，喷嘴直径为4mm；含氟涂覆组合物按重量份计，包含偏氟乙烯均聚物10份、全氟辛基磺酸钾4份和水40份，涂覆操作条件为使用振动筛，操作温度为45℃，振动频率为40HZ，喷枪气压控制为0.4MPaG，喷嘴直径为4mm，超声频率为100KHZ。Select 3-5mm synthetic rubber particles B, wash and dry; spray and wet with oxalic acid solution with a mass fraction of 12%; the inorganic coating composition, in parts by weight, contains aluminum oxide nanoparticles with a D90 of 185nm. 15 parts of particles, 15 parts of polyurethane emulsion, 4 parts of vinyltrimethoxysilane, 6 parts of polyoxyethylene ether, 6 parts of cellulose derivatives, and 6 parts of water, the coating operating conditions are the use of ultrasonic vibrating screen, and the operating temperature is 85°C, the ultrasonic frequency is 100KHZ, the vibration frequency is 80HZ, the air pressure of the spray gun is controlled at 0.4MPaG, and the diameter of the nozzle is 4mm; the fluorine-containing coating composition, in parts by weight, comprises 10 parts of vinylidene fluoride homopolymer, perfluorooctyl 4 parts of potassium sulfonate and 40 parts of water, the coating operating conditions are vibrating screen, operating temperature is 45°C, vibration frequency is 40HZ, air pressure control of spray gun is 0.4MPaG, nozzle diameter is 4mm, and ultrasonic frequency is 100KHZ.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为3.96mm，包覆层的厚度为63.7微米，内核的氟元素含量(原子％)为5.94％，包覆层的氟元素含量(原子％)为60.23％，包覆橡胶颗粒的24h吸油率为2.7％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为2.09，包覆层的高价金属含量(原子％)为0.23％，内核的高价金属含量(原子％)为0.11％，包覆层的金属碳比A(原子比)为0.0063，内核的金属碳比B(原子比)为0.0015，金属碳比A与所述金属碳比B的比例为4.2，包覆层的氟碳比(原子比)为1.66， 内核的氟碳比(原子比)为0.08。The obtained coated rubber particles were analyzed and tested, and the average particle size was 3.96 mm, the thickness of the coating layer was 63.7 microns, the fluorine element content (atomic %) of the inner core was 5.94%, and the fluorine element content (atomic %) of the coating layer was 5.94%. %) was 60.23%, and the 24h oil absorption rate of the coated rubber particles was 2.7%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2.09, the high-valent metal content (atomic %) of the cladding layer is 0.23%, and the high-valent metal content (atomic %) of the inner core is 0.11%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0063, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0015, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 4.2, the cladding The fluorocarbon ratio (atomic ratio) of the layer was 1.66, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.08.
实施例5制造的包覆橡胶颗粒的SEM照片见图1，可以明显区分包覆层和橡胶内核。对包覆层选择1和2两个位置，对橡胶内核选择3一个位置，图2给出了这三个位置的EDS能谱数据。The SEM photo of the coated rubber particles produced in Example 5 is shown in Figure 1, and the coating layer and the rubber core can be clearly distinguished. Two positions 1 and 2 are selected for the cladding layer, and one position 3 is selected for the rubber core. Figure 2 shows the EDS energy spectrum data of these three positions.
实施例6Example 6
选取1-3mm天然橡胶A及合成橡胶B复合颗粒，洗净、烘干；用质量分数为6％的丙三醇溶液喷淋、润湿；无机涂覆组合物按重量份计，包含D90为36nm的碳酸钙纳米颗粒30份、α-氰基丙烯酸乙酯乳液30份、乙烯基三乙氧基硅烷8份、烷基硫酸盐8份、聚丙烯酰胺6份、以及水10份，涂覆操作条件为使用超声振动筛，操作温度为60℃，超声频率为50KHZ，振动频率为35HZ，喷枪气压控制为0.4MPaG，喷嘴直径为4mm；含氟涂覆组合物按重量份计，包含四氟乙烯均聚物8份、全氟辛基磺酸钾4份和水25份，涂覆操作条件为使用振动筛，操作温度为35℃，振动频率为45HZ，喷枪气压控制为0.4MPaG，喷嘴直径为4mm，超声频率为50KHZ。Select 1-3mm composite particles of natural rubber A and synthetic rubber B, wash and dry; spray and wet with a glycerin solution whose mass fraction is 6%; the inorganic coating composition, in parts by weight, contains D90 as 30 parts of 36nm calcium carbonate nanoparticles, 30 parts of ethyl alpha-cyanoacrylate emulsion, 8 parts of vinyltriethoxysilane, 8 parts of alkyl sulfate, 6 parts of polyacrylamide, and 10 parts of water, coated The operating conditions are to use an ultrasonic vibrating screen, the operating temperature is 60°C, the ultrasonic frequency is 50KHZ, the vibration frequency is 35HZ, the air pressure of the spray gun is 0.4MPaG, and the diameter of the nozzle is 4mm; the fluorine-containing coating composition is based on parts by weight. 8 parts of ethylene homopolymer, 4 parts of potassium perfluorooctane sulfonate and 25 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 35°C, the vibration frequency is 45HZ, the air pressure of the spray gun is controlled to 0.4MPaG, and the diameter of the nozzle is is 4mm, and the ultrasonic frequency is 50KHZ.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为2.46mm，包覆层的厚度为273.8微米内核的氟元素含量(原子％)为3.7％，包覆层的氟元素含量(原子％)为63.2％，包覆橡胶颗粒的24h吸油率为2.5％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为3.09，包覆层的高价金属含量(原子％)为0.34％，内核的高价金属含量(原子％)为0.11％，包覆层的金属碳比A(原子比)为0.0099，内核的金属碳比B(原子比)为0.0027，金属碳比A与所述金属碳比B的比例为3.67，包覆层的氟碳比(原子比)为1.84，内核的氟碳比(原子比)为0.09。The obtained coated rubber particles were analyzed and tested, and the average particle size was 2.46 mm. The thickness of the coating layer was 273.8 microns. ) was 63.2%, and the 24h oil absorption rate of the coated rubber particles was 2.5%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core was 3.09, the high-valent metal content (atomic %) of the cladding layer was 0.34%, and the high-valent metal content (atomic %) of the inner core was 0.34% is 0.11%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0099, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0027, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.67. The fluorocarbon ratio (atomic ratio) of the layer was 1.84, and the fluorocarbon ratio (atomic ratio) of the core was 0.09.
实施例7Example 7
选取3-5mm天然橡胶A及合成橡胶B复合颗粒，洗净、烘干；用质量分数为6％的乙二酸溶液喷淋、润湿；无机涂覆组合物按重量份计，包含D90为36nm的碳酸钙纳米颗粒20份、聚醋酸乙烯酯系乳液20份、乙烯基三甲氧基硅烷5份、烷基硫酸盐5份、聚丙烯酸盐5份、以及水5份，涂覆操作条件为使用超声振动筛，操作温度为50℃，超声频率为50KHZ，振动频率为35HZ，喷枪气压控 制为0.3MPaG，喷嘴直径为8mm；含氟涂覆组合物按重量份计，包含四氟乙烯均聚物8份、全氟辛基磺酸钾3份和水30份，涂覆操作条件为使用振动筛，操作温度为35℃，振动频率为45HZ，喷枪气压控制为0.3MPaG，喷嘴直径为8mm，超声频率为50KHZ。Select 3-5mm composite particles of natural rubber A and synthetic rubber B, wash and dry; spray and wet with an oxalic acid solution with a mass fraction of 6%; the inorganic coating composition, in parts by weight, contains D90 as 20 parts of calcium carbonate nanoparticles of 36 nm, 20 parts of polyvinyl acetate emulsion, 5 parts of vinyltrimethoxysilane, 5 parts of alkyl sulfate, 5 parts of polyacrylate, and 5 parts of water, and the coating operation conditions are: Using an ultrasonic vibrating screen, the operating temperature is 50°C, the ultrasonic frequency is 50KHZ, the vibration frequency is 35HZ, the air pressure of the spray gun is controlled to 0.3MPaG, and the diameter of the nozzle is 8mm; the fluorine-containing coating composition is based on parts by weight, comprising tetrafluoroethylene homopolymer 8 parts of materials, 3 parts of potassium perfluorooctane sulfonate and 30 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 35°C, the vibration frequency is 45HZ, the air pressure of the spray gun is 0.3MPaG, and the nozzle diameter is 8mm, The ultrasonic frequency is 50KHZ.
对制得的包覆橡胶颗粒分析测试可得，内核的氟元素含量(原子％)为3.9％，包覆层的氟元素含量(原子％)为68.1％，包覆橡胶颗粒的24h吸油率为1.8％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为2.9，包覆层的高价金属含量(原子％)为0.29％，内核的高价金属含量(原子％)为0.10％，包覆层的金属碳比A(原子比)为0.0099，内核的金属碳比B(原子比)为0.0021，金属碳比A与所述金属碳比B的比例为4.71，包覆层的氟碳比(原子比)为2.33，内核的氟碳比(原子比)为0.08。According to the analysis and test of the prepared coated rubber particles, the content of fluorine element in the inner core (at %) is 3.9%, the content of fluorine element in the coating layer (at %) is 68.1%, and the 24h oil absorption rate of the coated rubber particles is 1.8%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2.9, the high-valent metal content (atomic %) of the cladding layer is 0.29%, and the high-valent metal content (atomic %) of the inner core is 0.10%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0099, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0021, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 4.71, the cladding The fluorocarbon ratio (atomic ratio) of the layer was 2.33, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.08.
实施例8Example 8
选取1-3mm合成橡胶颗粒B，洗净、烘干；用质量分数为10％的乙二醇溶液喷淋、润湿；无机涂覆组合物按重量份计，包含D90为167nm的硅铝纳米颗粒18份、聚丙烯酸酯系乳液15份、乙烯基三(β-甲氧乙氧基)硅烷4份、聚乙二醇4份、聚丙烯酸盐3份、以及水5份，涂覆操作条件为使用超声振动筛，操作温度为60℃，超声频率为20KHZ，振动频率为30HZ，喷枪气压控制为0.2MPaG，喷嘴直径为10mm；含氟涂覆组合物按重量份计，包含六氟乙烯均聚物5份、全氟辛基磺酸钾2份和水25份，涂覆操作条件为使用振动筛，操作温度为30℃，振动频率为30HZ，喷枪气压控制为0.2MPaG，喷嘴直径为10mm，超声频率为20KHZ。Select 1-3mm synthetic rubber particles B, wash and dry; spray and wet with ethylene glycol solution with a mass fraction of 10%; the inorganic coating composition is based on parts by weight, comprising silicon-alumina nanometers with D90 of 167nm 18 parts of particles, 15 parts of polyacrylate emulsion, 4 parts of vinyl tris (β-methoxyethoxy) silane, 4 parts of polyethylene glycol, 3 parts of polyacrylate, and 5 parts of water, coating operating conditions In order to use the ultrasonic vibrating screen, the operating temperature is 60°C, the ultrasonic frequency is 20KHZ, the vibration frequency is 30HZ, the air pressure of the spray gun is controlled to be 0.2MPaG, and the diameter of the nozzle is 10mm; 5 parts of polymer, 2 parts of potassium perfluorooctane sulfonate and 25 parts of water, the coating operation conditions are to use a vibrating screen, the operating temperature is 30 ° C, the vibration frequency is 30 Hz, the air pressure of the spray gun is controlled to 0.2 MPaG, and the diameter of the nozzle is 10 mm , the ultrasonic frequency is 20KHZ.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为2.17mm，包覆层的厚度为269.2微米，内核的氟元素含量(原子％)为5.3％，包覆层的氟元素含量(原子％)为54.9％，包覆橡胶颗粒的24h吸油率为2.6％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为2.25，包覆层的高价金属含量(原子％)为0.27％，内核的高价金属含量(原子％)为0.12％，包覆层的金属碳比A(原子比)为0.0064，内核的金属碳比B(原子比)为0.003，金属碳比A与所述金属碳比B的比例为2.13，包覆层的氟碳比(原子比)为1.3，内核的氟碳比(原子比)为0.13。The obtained coated rubber particles were analyzed and tested, and the average particle size was 2.17 mm, the thickness of the coating layer was 269.2 microns, the fluorine element content (atomic %) of the inner core was 5.3%, and the fluorine element content (atomic %) of the coating layer was 5.3%. %) was 54.9%, and the 24h oil absorption rate of the coated rubber particles was 2.6%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2.25, the high-valent metal content (atomic %) of the cladding layer is 0.27%, and the high-valent metal content (atomic %) of the inner core is 0.12%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0064, the metal-carbon ratio B (atomic ratio) of the inner core is 0.003, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 2.13. The fluorocarbon ratio (atomic ratio) of the layer was 1.3, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.13.
实施例9Example 9
选取1-3mm合成橡胶颗粒B，洗净、烘干；用质量分数为8％的丙三醇溶液喷淋、润湿；无机涂覆组合物按重量份计，包含D90为75nm的碳酸钙纳米颗粒25份、聚醋酸乙烯酯系乳液20份、松香乳胶5份、乙烯基三乙氧基硅烷5份、聚乙二醇5份、聚丙烯酸盐3份、以及水8份，涂覆操作条件为使用超声振动筛，操作温度为70℃，超声频率为20KHZ，振动频率为45HZ，喷枪气压控制为0.3MPaG，喷嘴直径为8mm；含氟涂覆组合物按重量份计，包含四氟乙烯均聚物10份、全氟辛基磺酸钾3份和水30份，涂覆操作条件为使用振动筛，操作温度为30℃，振动频率为45HZ，喷枪气压控制为0.3MPaG，喷嘴直径为8mm，超声频率为20KHZ。Select 1-3mm synthetic rubber particles B, wash and dry; spray and wet with a glycerin solution with a mass fraction of 8%; the inorganic coating composition, by weight, comprises calcium carbonate nanoparticles with a D90 of 75nm 25 parts of particles, 20 parts of polyvinyl acetate emulsion, 5 parts of rosin latex, 5 parts of vinyltriethoxysilane, 5 parts of polyethylene glycol, 3 parts of polyacrylate, and 8 parts of water, coating operation conditions In order to use the ultrasonic vibrating screen, the operating temperature is 70°C, the ultrasonic frequency is 20KHZ, the vibration frequency is 45HZ, the air pressure of the spray gun is controlled to be 0.3MPaG, and the diameter of the nozzle is 8mm; 10 parts of polymer, 3 parts of potassium perfluorooctane sulfonate and 30 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 30 ° C, the vibration frequency is 45HZ, the air pressure of the spray gun is 0.3MPaG, and the nozzle diameter is 8mm , the ultrasonic frequency is 20KHZ.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为2.83mm，包覆层的厚度为177.6微米，内核的氟元素含量(原子％)为6.3％，包覆层的氟元素含量(原子％)为57.8％，包覆橡胶颗粒的24h吸油率为1.7％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为6.17，包覆层的高价金属含量(原子％)为0.37％，内核的高价金属含量(原子％)为0.06％，包覆层的金属碳比A(原子比)为0.0096，内核的金属碳比B(原子比)为0.0021，金属碳比A与所述金属碳比B的比例为4.57，包覆层的氟碳比(原子比)为1.5，内核的氟碳比(原子比)为0.22。The obtained coated rubber particles were analyzed and tested, and the average particle size was 2.83 mm, the thickness of the coating layer was 177.6 microns, the fluorine element content (atomic %) of the inner core was 6.3%, and the fluorine element content (atomic %) of the coating layer was 6.3%. %) was 57.8%, and the 24h oil absorption rate of the coated rubber particles was 1.7%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core was 6.17, the high-valent metal content (atomic %) of the cladding layer was 0.37%, and the high-valent metal content (atomic %) of the inner core is 0.06%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0096, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0021, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 4.57, the cladding The fluorocarbon ratio (atomic ratio) of the layer was 1.5, and the fluorocarbon ratio (atomic ratio) of the core was 0.22.
实施例10Example 10
选取1-3mm合成橡胶颗粒B，洗净、烘干；用质量分数为5％的乙酸溶液和5％丙三醇溶液混合物喷淋、润湿；无机涂覆组合物按重量份计，包含D90为136nm的二氧化硅纳米颗粒22份、聚丙烯酸酯系乳液25份、乙烯基三乙氧基硅烷3份、烷基硫酸盐3份、纤维素硫酸钠4份、以及水5份，涂覆操作条件为使用超声振动筛，操作温度为45℃，超声频率为10KHZ，振动频率为20HZ，喷枪气压控制为0.2MPaG，喷嘴直径为10mm；含氟涂覆组合物按重量份计，包含四氟乙烯共聚物6份、全氟辛酸铵3份和水35份，涂覆操作条件为使用振动筛，操作温度为30℃，振动频率为40HZ，喷枪气压控制为0.2MPaG，喷嘴直径为10mm，超声频率为20KHZ。Select 1-3mm synthetic rubber particles B, wash and dry; spray and wet with a mixture of 5% acetic acid solution and 5% glycerol solution by mass fraction; the inorganic coating composition, in parts by weight, contains D90 22 parts of 136nm silica nanoparticles, 25 parts of polyacrylate emulsion, 3 parts of vinyltriethoxysilane, 3 parts of alkyl sulfate, 4 parts of sodium cellulose sulfate, and 5 parts of water, coated The operating conditions are to use an ultrasonic vibrating screen, the operating temperature is 45°C, the ultrasonic frequency is 10KHZ, the vibration frequency is 20HZ, the air pressure of the spray gun is controlled at 0.2MPaG, and the diameter of the nozzle is 10mm; the fluorine-containing coating composition is based on parts by weight. 6 parts of ethylene copolymer, 3 parts of ammonium perfluorooctanoate and 35 parts of water, the coating operating conditions are using a vibrating screen, the operating temperature is 30°C, the vibration frequency is 40HZ, the air pressure control of the spray gun is 0.2MPaG, the diameter of the nozzle is 10mm, and the ultrasonic frequency is 20KHZ.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为2.58mm，包覆层的厚度为257.4微米，内核的氟元素含量(原子％)为5.9％，包覆层的氟元素含量(原子％)为61.1％，包覆橡胶颗粒的24h吸油率为2.3％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为2，包覆层的高价金属含量(原子％)为0.26％，内核的高价金属含量(原子％)为0.13％，包覆层的金属碳比A(原子比)为0.0072，内核的金属碳比B(原子比)为0.0026，金属碳比A与所述金属碳比B的比例为2.77，包覆层的氟碳比(原子比)为1.7，内核的氟碳比(原子比)为0.12。The obtained coated rubber particles were analyzed and tested, and the average particle size was 2.58 mm, the thickness of the coating layer was 257.4 microns, the fluorine element content (atomic %) of the inner core was 5.9%, and the fluorine element content (atomic %) of the coating layer was 5.9%. %) was 61.1%, and the 24h oil absorption rate of the coated rubber particles was 2.3%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2, the high-valent metal content (atomic %) of the cladding layer is 0.26%, the high-valent metal content of the inner core (atomic %) is 0.13%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0072, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0026, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 2.77. The fluorocarbon ratio (atomic ratio) of the layer was 1.7, and the fluorocarbon ratio (atomic ratio) of the core was 0.12.
实施例11Example 11
选取1-3mm天然橡胶颗粒A，洗净、烘干；用质量分数为5％的乙酸溶液喷淋、润湿；无机涂覆组合物按重量份计，包含D90为75nm的碳酸钙纳米颗粒15份、聚丙烯酸酯系乳液20份、乙烯基三乙氧基硅烷2份、聚乙二醇2份、聚丙烯酸盐2份、以及水2份，涂覆操作条件为使用超声振动筛，操作温度为40℃，超声频率为10KHZ，振动频率为20HZ，喷枪气压控制为0.1MPaG，喷嘴直径为20mm。Select 1-3mm natural rubber particles A, wash, dry; spray and wet with acetic acid solution with a mass fraction of 5%; the inorganic coating composition, by weight, comprises calcium carbonate nanoparticles with D90 of 75nm 15 parts, 20 parts of polyacrylate emulsion, 2 parts of vinyltriethoxysilane, 2 parts of polyethylene glycol, 2 parts of polyacrylate, and 2 parts of water, the coating operating conditions are the use of ultrasonic vibrating screen, the operating temperature The temperature is 40℃, the ultrasonic frequency is 10KHZ, the vibration frequency is 20HZ, the air pressure of the spray gun is controlled to 0.1MPaG, and the diameter of the nozzle is 20mm.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为2.77mm，包覆层的厚度为74.6微米，包覆橡胶颗粒的24h吸油率为5.7％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为3.5，包覆层的高价金属含量(原子％)为0.14％，内核的高价金属含量(原子％)为0.04％，包覆层的金属碳比A(原子比)为0.0042，内核的金属碳比B(原子比)为0.0013，金属碳比A与所述金属碳比B的比例为3.23。The obtained coated rubber particles were analyzed and tested, and the average particle size was 2.77 mm, the thickness of the coating layer was 74.6 microns, and the 24-hour oil absorption rate of the coated rubber particles was 5.7%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core was 3.5, the high-valent metal content (atomic %) of the cladding layer was 0.14%, and the high-valent metal content (atomic %) of the inner core was 0.14%. The metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0042, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0013, and the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.23.
实施例12Example 12
选取1-3mm天然橡胶颗粒A，洗净、烘干；用质量分数为5％的乙酸溶液喷淋、润湿；含氟涂覆组合物按重量份计，包含四氟乙烯均聚物3份、全氟辛基磺酸钾1份和水20份，涂覆操作条件为使用振动筛，操作温度为30℃，振动频率为40HZ，喷枪气压控制为0.1MPaG，喷嘴直径为20mm，超声频率为20KHZ。Select 1-3mm natural rubber particles A, wash and dry; spray and wet with acetic acid solution with a mass fraction of 5%; the fluorine-containing coating composition, in parts by weight, contains 3 parts of tetrafluoroethylene homopolymer , 1 part of potassium perfluorooctane sulfonate and 20 parts of water, the coating operating conditions are to use a vibrating screen, the operating temperature is 30 ° C, the vibration frequency is 40HZ, the air pressure control of the spray gun is 0.1MPaG, the diameter of the nozzle is 20mm, and the ultrasonic frequency is 20KHZ.
对制得的包覆橡胶颗粒分析测试可得，平均粒度为2.62mm，包覆层的厚度为217.5微米，内核的氟元素含量(原子％)为0％，包覆层的氟元素含量(原 子％)为63.3％，包覆橡胶颗粒的24h吸油率为3.9％。包覆层的高价金属含量(原子％)与内核的高价金属含量(原子％)之比为2.2，包覆层的高价金属含量(原子％)为0.11％，内核的高价金属含量(原子％)为0.05％，包覆层的金属碳比A(原子比)为0.0031，内核的金属碳比B(原子比)为0.0008，金属碳比A与所述金属碳比B的比例为3.88，包覆层的氟碳比(原子比)为1.81，内核的氟碳比(原子比)为0。The obtained coated rubber particles were analyzed and tested, and the average particle size was 2.62 mm, the thickness of the coating layer was 217.5 microns, the fluorine element content (atomic %) of the inner core was 0%, and the fluorine element content (atomic %) of the coating layer was 0%. %) was 63.3%, and the 24h oil absorption rate of the coated rubber particles was 3.9%. The ratio of the high-valent metal content (atomic %) of the cladding layer to the high-valent metal content (atomic %) of the inner core is 2.2, the high-valent metal content (atomic %) of the cladding layer is 0.11%, and the high-valent metal content (atomic %) of the inner core is 0.11% is 0.05%, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.0031, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0008, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 3.88, the cladding The fluorocarbon ratio (atomic ratio) of the layer was 1.81, and the fluorocarbon ratio (atomic ratio) of the inner core was 0.
应用实施例1Application Example 1
向油基钻井液中加入质量分数为5％的实施例1制得的包覆橡胶颗粒，获得油基堵漏钻井液。The coated rubber particles prepared in Example 1 with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based drilling fluid for plugging losses.
应用实施例2Application Example 2
向油基钻井液中加入质量分数为5％的实施例9制得的包覆橡胶颗粒，获得油基堵漏钻井液。The coated rubber particles prepared in Example 9 with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based drilling fluid for plugging losses.
应用实施例3Application Example 3
向油基钻井液中加入质量分数为5％的实施例6制得的包覆橡胶颗粒，获得油基堵漏钻井液。The coated rubber particles prepared in Example 6 with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based lost circulation plugging drilling fluid.
应用实施例4Application Example 4
向油基钻井液中加入质量分数为3％的实施例2制得的包覆橡胶颗粒和质量分数为2％的实施例3制得的包覆橡胶颗粒，获得油基堵漏钻井液。The coated rubber particles prepared in Example 2 with a mass fraction of 3% and the coated rubber particles prepared in Example 3 with a mass fraction of 2% were added to the oil-based drilling fluid to obtain an oil-based plugging drilling fluid.
应用实施例5Application Example 5
向油基钻井液中加入质量分数为3％的实施例3制得的包覆橡胶颗粒和质量分数为2％的实施例4制得的包覆橡胶颗粒，获得油基堵漏钻井液。The coated rubber particles prepared in Example 3 with a mass fraction of 3% and the coated rubber particles prepared in Example 4 with a mass fraction of 2% were added to the oil-based drilling fluid to obtain an oil-based plugging drilling fluid.
应用实施例6Application Example 6
向油基钻井液中加入质量分数为3％的实施例4制得的包覆橡胶颗粒和质量分数为2％的实施例5制得的包覆橡胶颗粒，获得油基堵漏钻井液。The coated rubber particles prepared in Example 4 with a mass fraction of 3% and the coated rubber particles prepared in Example 5 with a mass fraction of 2% were added to the oil-based drilling fluid to obtain an oil-based plugging drilling fluid.
应用实施例7Application Example 7
向油基钻井液中加入质量分数为3％的实施例5制得的包覆橡胶颗粒和质量分数为2％的纤维状材料，获得油基堵漏钻井液。The coated rubber particles prepared in Example 5 with a mass fraction of 3% and fibrous materials with a mass fraction of 2% were added to the oil-based drilling fluid to obtain an oil-based lost circulation plugging drilling fluid.
应用实施例8Application Example 8
向油基钻井液中加入质量分数为3％的实施例6制得的包覆橡胶颗粒和质量分数为2％的纤维状材料，获得油基堵漏钻井液。The coated rubber particles prepared in Example 6 with a mass fraction of 3% and fibrous materials with a mass fraction of 2% were added to the oil-based drilling fluid to obtain an oil-based lost circulation plugging drilling fluid.
应用实施例9Application Example 9
向油基钻井液中加入质量分数为2％的实施例7制得的包覆橡胶颗粒、质量分数为2％的实施例8制得的包覆橡胶颗粒和质量分数为1％的纤维状材料，获得油基堵漏钻井液。To the oil-based drilling fluid, the coated rubber particles prepared in Example 7 with a mass fraction of 2%, the coated rubber particles prepared in Example 8 with a mass fraction of 2%, and a fibrous material with a mass fraction of 1% were added , to obtain oil-based plugging drilling fluid.
应用实施例10Application Example 10
向油基钻井液中加入质量分数为3％的实施例10制得的包覆橡胶颗粒、质量分数为1％的实施例7制得的包覆橡胶颗粒和质量分数为1％的纤维状材料，获得油基堵漏钻井液。The coated rubber particles prepared in Example 10 with a mass fraction of 3%, the coated rubber particles prepared in Example 7 with a mass fraction of 1%, and fibrous materials with a mass fraction of 1% were added to the oil-based drilling fluid , to obtain oil-based plugging drilling fluid.
应用实施例11Application Example 11
向油基钻井液中加入质量分数为5％的实施例11制得的包覆橡胶颗粒，获得油基堵漏钻井液。The coated rubber particles prepared in Example 11 with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based lost circulation plugging drilling fluid.
应用实施例12Application Example 12
向油基钻井液中加入质量分数为5％的实施例12制得的包覆橡胶颗粒，获得油基堵漏钻井液。The coated rubber particles prepared in Example 12 with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based lost circulation plugging drilling fluid.
对比例1Comparative Example 1
向油基钻井液中加入质量分数为5％的橡胶颗粒A，获得油基堵漏钻井液。The rubber particles A with a mass fraction of 5% were added to the oil-based drilling fluid to obtain the oil-based lost circulation plugging drilling fluid.
对比例2Comparative Example 2
向油基钻井液中加入质量分数为3％的橡胶颗粒A和质量分数为2％的纤维状材料，获得油基堵漏钻井液。To the oil-based drilling fluid, add rubber particles A with a mass fraction of 3% and fibrous materials with a mass fraction of 2% to obtain an oil-based plugging drilling fluid.
采用堵漏评价模拟实验装置考察实施例和对比例获得的油基堵漏钻井液的堵漏性能。实验方法是：取3L油基堵漏钻井液加入堵漏模拟装置中，评价对5mm×4mm缝宽的楔形裂缝的堵漏能力，实验温度150℃，实验压力5MPa，记录压力随时间的变化关系。The plugging performance of the oil-based plugging drilling fluids obtained in the examples and comparative examples was investigated by using a plugging evaluation simulation experiment device. The experimental method is: add 3L oil-based plugging drilling fluid into the plugging simulation device to evaluate the plugging ability of wedge-shaped fractures with a fracture width of 5mm × 4mm. .
表1 不同油基堵漏钻井液的堵漏性能Table 1 The plugging performance of different oil-based plugging drilling fluids
Figure PCTCN2021075349-appb-000001
Figure PCTCN2021075349-appb-000001
由表1数据可知，与对比例相比，采用本发明的包覆橡胶颗粒，在高温高压条件下，承压堵漏性能更好，长时间承压条件下压降更小，表明在油基钻井液中具有更好长期承压能力。由实验数据还可知，不同粒径的包覆颗粒复配或包覆颗粒与纤维类材料复配使用具有更好的承压效果，单纯使用3-5mm的包覆橡胶颗粒时，大颗粒很容易在5mm裂缝开口处形成堆积，无法进入裂缝内部，承压略低；而根据1/3-2/3架桥理论，1-3mm包覆橡胶颗粒容易进 入裂缝并在裂缝中架桥堆积，从而能够形成致密承压封堵层。It can be seen from the data in Table 1 that, compared with the comparative example, using the coated rubber particles of the present invention, under the condition of high temperature and high pressure, the leakage plugging performance under pressure is better, and the pressure drop is smaller under the condition of long-term pressure, indicating that under the condition of high temperature and high pressure, the pressure drop is smaller. The drilling fluid has better long-term pressure bearing capacity. It can also be seen from the experimental data that the combination of coated particles with different particle sizes or the combination of coated particles and fibrous materials has a better pressure bearing effect. When simply using 3-5mm coated rubber particles, large particles are easy to Accumulation is formed at the opening of the 5mm crack, which cannot enter the crack, and the bearing pressure is slightly lower; according to the 1/3-2/3 bridging theory, the 1-3mm coated rubber particles are easy to enter the crack and bridge and accumulate in the crack, thus A dense pressure-bearing sealing layer can be formed.

Claims (17)

  1. 一种包覆橡胶颗粒，具有橡胶内核和包覆层，其中所述内核的氟元素含量(原子％)为0-15％(优选0-8％)，所述包覆层的氟元素含量(原子％)为30-80％(优选40-65％)，并且所述包覆橡胶颗粒的24h吸油率为4％以下(优选3％以下，更优选1.5-2.5％)。A coated rubber particle having a rubber inner core and a coating layer, wherein the fluorine element content (atomic %) of the inner core is 0-15% (preferably 0-8%), and the fluorine element content of the coating layer ( atomic %) is 30-80% (preferably 40-65%), and the 24h oil absorption of the coated rubber particles is 4% or less (preferably 3% or less, more preferably 1.5-2.5%).
  2. 权利要求1所述的包覆橡胶颗粒，其中所述包覆层的高价金属含量(原子％)与所述内核的高价金属含量(原子％)之比为1-10(优选1.2-3)，和/或，所述高价金属选自铝、钙、钛、镁、钡和硅中的至少一种(优选选自钙和硅中的至少一种，特别是钙)，和/或，所述包覆层的高价金属含量(原子％)为0.15-0.50％(优选0.20-0.30％)，和/或，所述内核的高价金属含量(原子％)为0.05-0.2％(优选0.10-0.15％)，和/或，所述包覆层的金属碳比A(原子比)为0.003-0.01(优选0.004-0.008)，和/或，所述内核的金属碳比B(原子比)为0.0008-0.003(优选0.001-0.002)，和/或，所述金属碳比A与所述金属碳比B的比例为2-13(优选3-6)，和/或，所述包覆层的氟碳比(原子比)为1-3(优选1.2-1.8)，和/或，所述内核的氟碳比(原子比)为0-0.25(优选0-0.12)。The coated rubber particle of claim 1, wherein the ratio of the high-valent metal content (atomic %) of the coating layer to the high-valent metal content (atomic %) of the inner core is 1-10 (preferably 1.2-3), And/or, the high-valent metal is selected from at least one of aluminum, calcium, titanium, magnesium, barium and silicon (preferably selected from at least one of calcium and silicon, especially calcium), and/or, the The high-valent metal content (atomic %) of the cladding layer is 0.15-0.50% (preferably 0.20-0.30%), and/or the high-valent metal content (atomic %) of the inner core is 0.05-0.2% (preferably 0.10-0.15%) ), and/or, the metal-carbon ratio A (atomic ratio) of the cladding layer is 0.003-0.01 (preferably 0.004-0.008), and/or, the metal-carbon ratio B (atomic ratio) of the inner core is 0.0008- 0.003 (preferably 0.001-0.002), and/or, the ratio of the metal-carbon ratio A to the metal-carbon ratio B is 2-13 (preferably 3-6), and/or, the fluorocarbon of the coating layer The ratio (atomic ratio) is 1-3 (preferably 1.2-1.8), and/or the fluorocarbon ratio (atomic ratio) of the inner core is 0-0.25 (preferably 0-0.12).
  3. 权利要求1所述的包覆橡胶颗粒，其中所述橡胶选自天然橡胶、合成橡胶及其复合材料中的至少一种，和/或，所述包覆层包含无机颗粒(优选无机纳米颗粒，特别是选自碳酸钙纳米颗粒、二氧化硅纳米颗粒、氧化铝纳米颗粒和硅铝纳米颗粒中的至少一种)，和/或，所述包覆层包含含氟聚合物(优选氟代聚烯烃，特别是选自四氟乙烯均聚物、四氟乙烯共聚物、偏氟乙烯均聚物、偏氟乙烯共聚物、六氟丙烯均聚物和六氟丙烯共聚物中的至少一种)。The coated rubber particles of claim 1, wherein the rubber is selected from at least one of natural rubber, synthetic rubber and composite materials thereof, and/or, the coating layer comprises inorganic particles (preferably inorganic nanoparticles, In particular, at least one selected from the group consisting of calcium carbonate nanoparticles, silica nanoparticles, alumina nanoparticles and silica alumina nanoparticles), and/or the coating layer comprises a fluoropolymer (preferably a fluoropolymer olefins, especially at least one selected from the group consisting of tetrafluoroethylene homopolymers, tetrafluoroethylene copolymers, vinylidene fluoride homopolymers, vinylidene fluoride copolymers, hexafluoropropylene homopolymers and hexafluoropropylene copolymers) .
  4. 权利要求1所述的包覆橡胶颗粒，其中所述无机颗粒与所述内核的重量比为0.01-0.12(优选0.02-0.05)，和/或，所述含氟聚合物与所述内核的重量比为0.015-0.06(优选0.025-0.04)，和/或，所述包覆橡胶颗粒的平均粒度为0.5-20mm(优选1-5mm)，和/或，所述无机颗粒的平均粒度为10-500nm(优选50-300nm或50-200nm)，和/或，所述包覆层的厚度使得与不具有所述包覆层的情况相比，所述包覆橡胶颗粒的24h吸油率降低20％以上(优选降低30％以上，更优选降低35-60％)，优选所述包覆层的厚度为0.05-500微米(优选1-300微米或20-200微米)，和/或，与不具有所述包覆层的情况相比，所述 包覆橡胶颗粒的24h吸油率降低20％以上(优选降低30％以上，更优选降低35-60％)。The coated rubber particles of claim 1, wherein the weight ratio of the inorganic particles to the inner core is 0.01-0.12 (preferably 0.02-0.05), and/or the weight of the fluoropolymer to the inner core The ratio is 0.015-0.06 (preferably 0.025-0.04), and/or the average particle size of the coated rubber particles is 0.5-20mm (preferably 1-5mm), and/or the average particle size of the inorganic particles is 10- 500nm (preferably 50-300nm or 50-200nm), and/or the thickness of the coating layer is such that the 24h oil absorption rate of the coated rubber particles is reduced by 20% compared to the case without the coating layer above (preferably reduced by more than 30%, more preferably reduced by 35-60%), preferably the thickness of the coating layer is 0.05-500 microns (preferably 1-300 microns or 20-200 microns), and/or, with no Compared with the case of the coating layer, the 24-hour oil absorption rate of the coated rubber particles is reduced by more than 20% (preferably by more than 30%, more preferably by 35-60%).
  5. 一种包覆橡胶颗粒的制造方法，包括以下步骤：A manufacturing method of coated rubber particles, comprising the following steps:
    (1)提供橡胶颗粒，和(1) provide rubber pellets, and
    (2)用选自无机颗粒和含氟聚合物的至少一者(优选两者)涂覆(优选喷涂或喷淋)所述橡胶颗粒，获得所述包覆橡胶颗粒。(2) Coating (preferably spraying or spraying) the rubber particles with at least one (preferably both) selected from inorganic particles and fluoropolymers to obtain the coated rubber particles.
  6. 权利要求5所述的制造方法，其中所述步骤(2)包括：The manufacturing method of claim 5, wherein the step (2) comprises:
    (2-1)用所述无机颗粒进行所述涂覆(优选喷涂或喷淋)，然后干燥或不干燥(优选不干燥)，和(优选然后)，(2-1) The coating (preferably spraying or spraying) with the inorganic particles, followed by drying or not (preferably not drying), and (preferably then),
    (2-2)用所述含氟聚合物进行所述涂覆(优选喷涂或喷淋)，然后干燥或不干燥(优选不干燥)。(2-2) The coating is performed with the fluoropolymer (preferably by spraying or spraying), and then dried or not (preferably not dried).
  7. 权利要求5所述的制造方法，其中所述含氟聚合物是氟代聚烯烃，特别是选自四氟乙烯均聚物、四氟乙烯共聚物、偏氟乙烯均聚物、偏氟乙烯共聚物、六氟丙烯均聚物和六氟丙烯共聚物中的至少一种，和/或，所述无机颗粒是无机纳米颗粒，特别是选自碳酸钙纳米颗粒、二氧化硅纳米颗粒、氧化铝纳米颗粒和硅铝纳米颗粒中的至少一种，和/或，所述橡胶选自天然橡胶、合成橡胶及其复合材料中的至少一种，和/或，所述橡胶颗粒的平均粒度为0.5-20mm(优选1-5mm)，和/或，所述无机颗粒的平均粒度为10-500nm(优选50-300nm或50-200nm)，和/或，所述橡胶颗粒包括废弃橡胶颗粒。The manufacturing method of claim 5, wherein the fluoropolymer is a fluoropolyolefin, in particular selected from the group consisting of tetrafluoroethylene homopolymer, tetrafluoroethylene copolymer, vinylidene fluoride homopolymer, vinylidene fluoride copolymer At least one of hexafluoropropylene homopolymer and hexafluoropropylene copolymer, and/or, the inorganic particles are inorganic nanoparticles, especially selected from calcium carbonate nanoparticles, silica nanoparticles, alumina nanoparticles At least one of nanoparticles and silica-alumina nanoparticles, and/or, the rubber is selected from at least one of natural rubber, synthetic rubber and composite materials thereof, and/or, the average particle size of the rubber particles is 0.5 -20mm (preferably 1-5mm), and/or, the inorganic particles have an average particle size of 10-500nm (preferably 50-300nm or 50-200nm), and/or, the rubber particles include waste rubber particles.
  8. 权利要求5所述的制造方法，其中所述无机颗粒以含有所述无机颗粒的涂覆组合物(称为无机涂覆组合物)的形式使用，和/或，所述含氟聚合物以含有所述含氟聚合物的涂覆组合物(称为含氟涂覆组合物)的形式使用。The manufacturing method of claim 5, wherein the inorganic particles are used in the form of a coating composition containing the inorganic particles (referred to as an inorganic coating composition), and/or the fluoropolymer is used in the form of a coating composition containing the inorganic particles. The fluoropolymer is used in the form of a coating composition (referred to as a fluorine-containing coating composition).
  9. 权利要求8所述的制造方法，其中所述无机涂覆组合物包含所述无机颗粒、粘结剂(优选聚合物乳液，特别是选自聚丙烯酸酯系乳液、聚醋酸乙烯酯系乳液、α-氰基丙烯酸乙酯乳液、环氧树脂乳液、聚氨酯乳液和松香乳胶中的至少一种，更特别是聚醋酸乙烯酯系乳液)、任选的偶联剂(优选硅烷偶联剂，更优选选自乙烯基三C1-6烷氧基(优选三C1-4烷氧基)硅烷中的至少一种，特别是选自乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷和乙烯基三(β-甲氧乙氧基)硅烷中的至少一种)、任选的润湿剂(优选选自聚乙二醇、烷基硫酸盐、有机磺酸盐和聚氧乙烯醚中的至少一种，更优选选自聚乙二醇 和烷基硫酸盐中的至少一种)、任选的分散剂(优选选自聚丙烯酸盐、纤维素衍生物、聚丙烯酰胺和聚氧乙烯醚磷酸酯盐中的至少一种，更优选纤维素硫酸钠)、以及任选的媒介(优选水)，和/或，所述含氟涂覆组合物包含所述含氟聚合物、分散剂(优选表面活性剂，特别是选自全氟辛基磺酸钾和全氟辛酸铵中的至少一种，更优选全氟辛基磺酸钾)和媒介(优选水)。The manufacturing method of claim 8, wherein the inorganic coating composition comprises the inorganic particles, a binder (preferably a polymer emulsion, especially selected from the group consisting of polyacrylate emulsions, polyvinyl acetate emulsions, alpha - at least one of ethyl cyanoacrylate emulsion, epoxy resin emulsion, polyurethane emulsion and rosin emulsion, more particularly polyvinyl acetate emulsion), optional coupling agent (preferably silane coupling agent, more preferably At least one selected from vinyltri-C1-6 alkoxy (preferably tri-C1-4 alkoxy) silanes, especially selected from vinyltriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane (at least one of beta-methoxyethoxy)silane), optional wetting agent (preferably at least one selected from polyethylene glycol, alkyl sulfate, organic sulfonate, and polyoxyethylene ether) species, more preferably selected from at least one of polyethylene glycols and alkyl sulfates), optional dispersants (preferably selected from polyacrylates, cellulose derivatives, polyacrylamides and polyoxyethylene ether phosphates) at least one of, more preferably sodium cellulose sulfate), and an optional vehicle (preferably water), and/or, the fluoropolymer coating composition comprises the fluoropolymer, a dispersant (preferably a surface active agent) agent, especially at least one selected from potassium perfluorooctane sulfonate and ammonium perfluorooctanoate, more preferably potassium perfluorooctane sulfonate) and vehicle (preferably water).
  10. 权利要求9所述的制造方法，其中以重量份计，所述无机涂覆组合物包含所述无机颗粒10-50重量份(优选15-25重量份)、所述粘结剂10-30重量份(优选20-30重量份)、所述任选的偶联剂0-10重量份(优选2-5重量份)、所述任选的润湿剂0-10重量份(优选2-5重量份)、所述任选的分散剂0-10重量份(优选2-5重量份)、以及所述任选的媒介0-10重量份(优选2-5重量份)，和/或，以重量份计，所述含氟涂覆组合物包含所述含氟聚合物3-15重量份(优选5-10重量份)、所述分散剂1-8重量份(优选1-3重量份)和所述媒介20-50重量份(优选25-40重量份)。The manufacturing method of claim 9, wherein in parts by weight, the inorganic coating composition comprises 10-50 parts by weight (preferably 15-25 parts by weight) of the inorganic particles and 10-30 parts by weight of the binder parts (preferably 20-30 parts by weight), 0-10 parts by weight (preferably 2-5 parts by weight) of the optional coupling agent, 0-10 parts by weight (preferably 2-5 parts by weight) of the optional wetting agent parts by weight), 0-10 parts by weight (preferably 2-5 parts by weight) of the optional dispersant, and 0-10 parts by weight (preferably 2-5 parts by weight) of the optional medium, and/or, In parts by weight, the fluorine-containing coating composition comprises 3-15 parts by weight (preferably 5-10 parts by weight) of the fluoropolymer, 1-8 parts by weight (preferably 1-3 parts by weight) of the dispersant ) and the medium 20-50 parts by weight (preferably 25-40 parts by weight).
  11. 权利要求5所述的制造方法，其中在所述步骤(1)与所述步骤(2)之间还包括润湿步骤：用润湿剂(优选选自羧酸和醇中的至少一种，更优选选自水易溶性羧酸和水易溶性醇中的至少一种，特别是选自C1-6一元或多元羧酸和C1-6一元或多元醇中的至少一种，更特别是选自乙酸和甘油中的至少一种)对所述橡胶颗粒进行处理(优选通过喷涂或喷淋)，然后干燥或不干燥(优选不干燥)。The manufacturing method of claim 5, wherein between the step (1) and the step (2), a wetting step is also included: with a wetting agent (preferably selected from at least one of carboxylic acids and alcohols, More preferably at least one selected from water-soluble carboxylic acids and water-soluble alcohols, especially at least one selected from C1-6 mono- or polycarboxylic acids and C1-6 mono- or polyhydric alcohols, more particularly selected The rubber particles are treated (preferably by spraying or spraying) from at least one of acetic acid and glycerol) and then dried or not (preferably not dried).
  12. 权利要求11所述的制造方法，其中所述润湿剂以含有所述润湿剂的组合物(称为润湿剂组合物)的形式使用，并且所述润湿剂组合物包含所述润湿剂和水。The manufacturing method of claim 11, wherein the wetting agent is used in the form of a composition containing the wetting agent (referred to as a wetting agent composition), and the wetting agent composition comprises the wetting agent Wetting agent and water.
  13. 权利要求12所述的制造方法，其中以重量份计，所述润湿剂组合物包含所述润湿剂2-15重量份(优选3-10重量份)和水98-85重量份(优选90-97重量份)，和/或，所述润湿剂与所述橡胶颗粒的重量比为0.01-0.05(优选0.02-0.035)。The manufacturing method of claim 12, wherein in parts by weight, the wetting agent composition comprises 2-15 parts by weight (preferably 3-10 parts by weight) of the wetting agent and 98-85 parts by weight (preferably 90-97 parts by weight), and/or, the weight ratio of the wetting agent to the rubber particles is 0.01-0.05 (preferably 0.02-0.035).
  14. 权利要求6所述的制造方法，其中所述步骤(2-1)的操作条件包括：喷涂或喷淋法，使用超声振动筛，操作温度为40-85℃(优选45-70℃或55-60℃)，超声频率为5-100KHZ(优选10-50KHZ或20-30KHZ)，振动频率为10-100HZ(优选25-75HZ或45-55HZ)，喷枪气压控制为0.1-0.5MPaG(优选 0.2-0.3MPaG)，喷嘴直径为2-20mm(优选5-10mm)，和/或，所述步骤(2-2)的操作条件包括：喷涂或喷淋法，使用振动筛，操作温度为20-45℃(优选30-35℃)，振动频率为10-100HZ(优选25-75HZ或45-55HZ)，喷枪气压控制为0.1-0.5MPaG(优选0.2-0.3MPaG)，喷嘴直径为2-20mm(优选5-10mm)，无超声或超声频率为5-100KHZ(优选10-50KHZ或20-30KHZ)。The manufacturing method according to claim 6, wherein the operating conditions of the step (2-1) include: spraying or spraying method, using an ultrasonic vibrating screen, and the operating temperature is 40-85 ℃ (preferably 45-70 ℃ or 55- 60℃), the ultrasonic frequency is 5-100KHZ (preferably 10-50KHZ or 20-30KHZ), the vibration frequency is 10-100HZ (preferably 25-75HZ or 45-55HZ), and the air pressure of the spray gun is 0.1-0.5MPaG (preferably 0.2- 0.3MPaG), the diameter of the nozzle is 2-20mm (preferably 5-10mm), and/or, the operating conditions of the step (2-2) include: spraying or spraying, using a vibrating screen, and an operating temperature of 20-45 ℃ (preferably 30-35 ℃), the vibration frequency is 10-100HZ (preferably 25-75HZ or 45-55HZ), the air pressure of the spray gun is controlled to be 0.1-0.5MPaG (preferably 0.2-0.3MPaG), and the diameter of the nozzle is 2-20mm (preferably 5-10mm), no ultrasound or the ultrasound frequency is 5-100KHZ (preferably 10-50KHZ or 20-30KHZ).
  15. 权利要求5所述的制造方法，其中所述无机颗粒与所述橡胶颗粒的重量比为0.01-0.12(优选0.02-0.05)，和/或，所述含氟聚合物与所述橡胶颗粒的重量比为0.015-0.06(优选0.025-0.04)。The manufacturing method of claim 5, wherein the weight ratio of the inorganic particles to the rubber particles is 0.01-0.12 (preferably 0.02-0.05), and/or the weight of the fluoropolymer to the rubber particles The ratio is 0.015-0.06 (preferably 0.025-0.04).
  16. 一种钻井液组合物(优选油基钻井液组合物)，包含堵漏材料和基浆(比如选自白油基钻井液基浆、柴油基钻井液基浆和合成基钻井液基浆中的至少一种)，其中所述堵漏材料包含或者是权利要求1所述的包覆橡胶颗粒或按照权利要求5所述的制造方法制造的包覆橡胶颗粒。A drilling fluid composition (preferably an oil-based drilling fluid composition) comprising a lost circulation material and a base slurry (such as at least one selected from the group consisting of white oil-based drilling fluid base slurry, diesel-based drilling fluid base slurry, and synthetic-based drilling fluid base slurry); a), wherein the leak-stopping material comprises either the coated rubber particles of claim 1 or the coated rubber particles manufactured according to the manufacturing method of claim 5.
  17. 权利要求16所述的钻井液组合物，其中以所述钻井液组合物的总质量为100wt％计，所述包覆橡胶颗粒的质量百分含量为2-12wt％(优选3-8wt％)。The drilling fluid composition according to claim 16, wherein the mass percentage of the coated rubber particles is 2-12 wt% (preferably 3-8 wt%) based on the total mass of the drilling fluid composition being 100 wt%. .
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